TWI666286B - Transparent adhesive sheet - Google Patents

Transparent adhesive sheet Download PDF

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TWI666286B
TWI666286B TW104126271A TW104126271A TWI666286B TW I666286 B TWI666286 B TW I666286B TW 104126271 A TW104126271 A TW 104126271A TW 104126271 A TW104126271 A TW 104126271A TW I666286 B TWI666286 B TW I666286B
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meth
acrylate
adhesive sheet
light
wavelength
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TW104126271A
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TW201614021A (en
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新美可保留
稲永誠
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日商三菱化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
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    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
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    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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    • C09J155/00—Adhesives based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09J123/00 - C09J153/00
    • C09J155/005—Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
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    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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    • C09J2451/00—Presence of graft polymer
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

本發明提供一種新之黏著片材，其係關於一種光硬化性之黏著片材，其即便存在印刷隱蔽部等光難以到達之部位，亦可進行光硬化，且即便為具有某程度厚度之黏著片材，亦可使片材整體硬化。 The invention provides a new adhesive sheet, which relates to a light-curing adhesive sheet, which can be light-hardened even if there is a place where light is difficult to reach, such as a printing concealed part, and even if it has a certain thickness of adhesion Sheets can also harden the entire sheet.

本發明提出一種透明黏著片材，其特徵係包含黏著劑組合物者，上述黏著劑組合物含有熱塑性樹脂(A)、交聯劑(B)、藉由至少波長380nm~430nm之光而反應之光聚合起始劑(C)、及被較波長380nm為短波長側之光激發而發出波長380nm~550nm之光之波長轉換劑(D)，其中波長390nm下之黏著片材之吸光度X與黏著片材之厚度Y滿足下述關係式(1)：式(1)...0.5≦X/Y≦12。 The present invention provides a transparent adhesive sheet, which is characterized in that it includes an adhesive composition. The adhesive composition contains a thermoplastic resin (A), a cross-linking agent (B), and reacts with light having a wavelength of at least 380 nm to 430 nm. Photopolymerization initiator (C), and a wavelength conversion agent (D) that is excited by light with a shorter wavelength side than 380nm and emits light with a wavelength of 380nm to 550nm, in which the absorbance X and adhesion of the adhesive sheet at a wavelength of 390nm The thickness Y of the sheet material satisfies the following relational expression (1): Expression (1) ... 0.5 ≦ X / Y ≦ 12.

Description

透明黏著片材 Transparent adhesive sheet

本發明係關於一種適於貼合圖像顯示裝置構成用構件之可光硬化之透明黏著片材。 The present invention relates to a light-curable transparent adhesive sheet suitable for bonding members constituting an image display device.

近年來，為提高圖像顯示裝置之視認性，進行有藉由利用接著劑填充液晶顯示器(LCD)、電漿顯示器(PDP)、電致發光顯示器(ELD)等之圖像顯示面板與配置於其前面側(視認側)之保護面板或觸控面板構件之間的空隙，而抑制入射光或來自顯示圖像之出射光於空氣層界面處之反射。 In recent years, in order to improve the visibility of image display devices, image display panels and liquid crystal displays (LCDs), plasma displays (PDPs), and electroluminescence displays (ELDs), which are filled with an adhesive, have been developed. The space between the front panel (viewing side) of the protective panel or the touch panel member suppresses the reflection of the incident light or the outgoing light from the display image at the interface of the air layer.

作為此種利用黏著劑填充圖像顯示裝置用構成構件間之空隙之方法，已知有如下方法：將包含紫外線硬化性樹脂之液狀之接著樹脂組合物填充於該空隙後，照射紫外線而使其硬化(專利文獻1)。 As such a method for filling a space between constituent members of an image display device with such an adhesive, a method is known in which a liquid adhesive resin composition containing an ultraviolet curable resin is filled in the space, and then ultraviolet rays are irradiated to It hardens (Patent Document 1).

又，亦已知有使用黏著片材填充圖像顯示裝置用構成構件間之空隙之方法。例如專利文獻2中，揭示有如下方法：將藉由紫外線進行1次交聯後之黏著片材貼合於圖像顯示裝置構成構件後，隔著圖像顯示裝置構成構件對黏著片材照射紫外線而使其2次硬化。 There is also known a method of filling a space between constituent members for an image display device with an adhesive sheet. For example, Patent Document 2 discloses a method in which an adhesive sheet that has been crosslinked by ultraviolet rays once is bonded to a constituent member of an image display device, and then the adhesive sheet is irradiated with ultraviolet rays through the constituent member of the image display device. It is then hardened twice.

專利文獻3中，揭示有如下方法：使用包含以重量平均分子量為2萬~10萬之(甲基)丙烯酸胺基甲酸酯為主成分且25℃下之損耗正切未達1之熱熔型之接著組合物的黏著片材，填充圖像顯示裝置用構成構件間之空隙。 Patent Document 3 discloses a method of using a hot-melt type containing a (meth) acrylic acid urethane having a weight average molecular weight of 20,000 to 100,000 as a main component and a loss tangent at 25 ° C of less than 1. The adhesive sheet of the composition is then adhered to fill the space between the constituent members for the image display device.

且說，於行動電話或移動終端等圖像顯示裝置中，通常於表面保 護面板之周緣部呈框狀地印刷隱蔽部。於如上所述般使用光硬化性之黏著劑或黏著片材接著圖像顯示裝置構成構件之情形時，若存在此種隱蔽部，則會產生為使黏著劑硬化而照射之紫外線難以到達之部位，因此，存在無法使該部分硬化而難以獲得穩定之品質之問題。 Moreover, in image display devices such as mobile phones or mobile terminals, The concealed portion is printed on the peripheral edge portion of the protective panel in a frame shape. In the case where a photocurable adhesive or an adhesive sheet is used as described above and then the image display device is constituted, if such a concealed portion is present, a part which is hard to reach by ultraviolet rays irradiated to harden the adhesive is generated. Therefore, there is a problem that the part cannot be hardened and it is difficult to obtain stable quality.

因此，例如專利文獻4(日本專利特開2013-184997號公報)中，作為即便於陰影部或狹隙部等亦可良好地硬化之液狀光硬化性樹脂組合物，揭示有包含含乙烯性不飽和鍵之成分、於370~420nm之範圍內具有極大吸收波長之光聚合起始劑、及螢光體之液狀光硬化性樹脂組合物。 Therefore, for example, in Patent Document 4 (Japanese Patent Laid-Open No. 2013-184997), as a liquid photocurable resin composition that can be cured well even in a shadow portion or a slit portion, it is disclosed that it contains ethylene-containing properties. A component of an unsaturated bond, a photopolymerization initiator having a maximum absorption wavelength in a range of 370 to 420 nm, and a liquid photocurable resin composition of a phosphor.

先前技術文獻 Prior art literature 專利文獻 Patent literature

專利文獻1：國際公開2010/027041號公報 Patent Document 1: International Publication No. 2010/027041

專利文獻2：日本專利第4971529號公報 Patent Document 2: Japanese Patent No. 4971529

專利文獻3：國際公開2010/038366號公報 Patent Document 3: International Publication No. 2010/038366

專利文獻4：日本專利特開2013-184997號公報 Patent Document 4: Japanese Patent Laid-Open No. 2013-184997

若如上述專利文獻4般使用液狀之紫外線硬化型接著劑接著圖像顯示裝置構成構件，則於塗佈或填充液體時容易產生厚度不均，調整或條件設置之作業變得繁雜，因此，存在生產性較差之問題。又，若調配螢光體，則接著劑樹脂組合物之透明性降低，因此，存在如下問題：若接著劑過厚，則有光無法到達接著劑之深部，反而硬化性降低之情形。進而，亦存在如下問題：於在過厚之部位或陰影部等產生接著劑之硬化不足之情形時，容易產生黏著劑漏出或腐蝕所接觸之構件等嚴重之不良情況。 If a liquid UV-curable adhesive is used to adhere to the components of the image display device as in the above-mentioned Patent Document 4, the thickness unevenness tends to occur when applying or filling the liquid, and the adjustment or setting of the conditions becomes complicated. There is a problem of poor productivity. In addition, if a phosphor is blended, the transparency of the adhesive resin composition is reduced. Therefore, if the adhesive is too thick, light may not reach the deep part of the adhesive, and the hardenability may be reduced. Furthermore, there is also a problem that when insufficient curing of the adhesive occurs in an excessively thick portion, a shadowed portion, or the like, serious problems such as leakage of the adhesive or corrosion of a contacted member are liable to occur.

另一方面，於將於常態下呈片狀之黏著片材用於圖像顯示裝置構 成構件之接著之情形時，即便為未硬化狀態，亦不會產生如黏著劑漏出般之嚴重之不良情況。然而，就靈活地追隨形成隱蔽部之印刷階差等而進入至各個角落，緩和黏著片材內產生之應變之觀點而言，對於黏著片材要求柔軟性或流動性。 On the other hand, an adhesive sheet that will be sheet-like in the normal state is used for the structure of an image display device. In the case where the component is adhered, even if it is in an unhardened state, a serious problem such as leakage of an adhesive does not occur. However, from the viewpoint of flexibly following the printing steps and the like forming the concealed portion and entering into various corners to ease the strain generated in the adhesive sheet, the adhesive sheet requires flexibility or fluidity.

因此，本發明係關於一種於常態下呈片狀之光硬化性之黏著片材，欲提供一種新之黏著片材，其即便存在印刷隱蔽部等光難以到達之部位，亦可進行光硬化，且即便為具有某程度之厚度之黏著片材，亦可使片材整體硬化。 Therefore, the present invention relates to a light-curing adhesive sheet that is sheet-like under normal conditions. To provide a new adhesive sheet that can be light-cured even if there is a light-accessible part such as a concealed printing part, And even if it is an adhesive sheet having a certain thickness, the entire sheet can be hardened.

本發明提出一種透明黏著片材，其特徵係包含黏著劑組合物者，上述黏著劑組合物含有熱塑性樹脂(A)、交聯劑(B)、藉由至少波長380nm~430nm之光而反應之光聚合起始劑(C)、及被較波長380nm為短波長側之光激發而發出波長380nm~550nm之光之波長轉換劑(D)，其中：波長390nm下之黏著片材之吸光度X與黏著片材之厚度Y滿足下述關係式(1)。 The present invention provides a transparent adhesive sheet, which is characterized in that it includes an adhesive composition. The adhesive composition contains a thermoplastic resin (A), a cross-linking agent (B), and reacts with light having a wavelength of at least 380 nm to 430 nm. Photopolymerization initiator (C), and a wavelength conversion agent (D) that emits light with a wavelength of 380nm to 550nm when excited by light at a shorter wavelength side than 380nm, of which: the absorbance X and The thickness Y of the adhesive sheet satisfies the following relational expression (1).

式(1)...0.5≦X/Y≦12 Equation (1) ... 0.5 ≦ X / Y ≦ 12

關於本發明所提出之透明黏著片材，若照射較波長380nm為短波長側之光、即例如“紫外線”，則波長轉換劑(D)被激發，而發出波長380nm~550nm之光、即例如“可見光”。藉由如上所述般波長轉換劑(D)於黏著片材內部發出可見光，而即便存在印刷隱蔽部等上述紫外線難以到達之部位，亦由於上述可見光會到達，故而可利用光聚合起始劑(C)進行光交聯而使其硬化。 Regarding the transparent adhesive sheet according to the present invention, if light with a shorter wavelength side than 380 nm is irradiated, that is, for example, "ultraviolet rays", the wavelength conversion agent (D) is excited to emit light with a wavelength of 380 nm to 550 nm, that is, for example, "Visible light". As described above, the wavelength conversion agent (D) emits visible light inside the adhesive sheet, and even if there is a hard-to-reach area such as a printing concealed portion, the visible light can reach the light, so a photopolymerization initiator ( C) Photocrosslinking to harden.

進而，藉由以黏著片材之吸光度X與厚度Y滿足上述關係式(1)之方式進行調整，而即便為具有某程度之厚度之黏著片材，光亦可到達黏著片材之深部，且上述可見光亦到達印刷隱蔽部等上述紫外線難以 到達之部位，因此可使片材整體硬化。 Furthermore, by adjusting the absorbance X and thickness Y of the adhesive sheet to satisfy the above-mentioned relational expression (1), even for an adhesive sheet having a certain thickness, light can reach the deep part of the adhesive sheet, and It is difficult for the visible light to reach the ultraviolet light, such as the concealed print It can harden the sheet as a whole.

繼而，對本發明之實施形態之一例進行說明。但，本發明不限定於下述實施形態。 Next, an example of an embodiment of the present invention will be described. However, the present invention is not limited to the following embodiments.

<本黏著片材> <This adhesive sheet>

本發明之實施形態之一例之透明黏著片材(以下稱作「本黏著片材」)係包含黏著劑組合物(稱作「本黏著劑組合物」)者，該黏著劑組合物含有熱塑性樹脂(A)、交聯劑(B)、藉由至少波長380nm~430nm之光而反應之光聚合起始劑(C)、及被較波長380nm為短波長側之光激發而發出波長380nm~550nm之光之波長轉換劑(D)。 The transparent adhesive sheet (hereinafter referred to as "the present adhesive sheet") which is an example of the embodiment of the present invention includes an adhesive composition (referred to as "the present adhesive composition"), and the adhesive composition contains a thermoplastic resin (A), a cross-linking agent (B), a photopolymerization initiator (C) that reacts with light having a wavelength of at least 380 nm to 430 nm, and emits a wavelength of 380 nm to 550 nm when excited by light having a shorter wavelength side than the wavelength of 380 nm Light wavelength conversion agent (D).

本黏著片材較佳為如下之黏著片材：於常態下可保持片狀，具有於未交聯狀態下進行加熱便熔融或流動之熱熔性，且具有可進行光交聯之光交聯性。 The adhesive sheet is preferably an adhesive sheet that can maintain a sheet shape in a normal state, has a hot-melt property that melts or flows when heated in an uncrosslinked state, and has a photocrosslinking that can be photocrosslinked. Sex.

若於常態下可保持片狀，則與液狀之接著劑相比，操作較容易，而且可省去填充液體之作業，因此，生產性尤其優異。 If the sheet can be maintained in a normal state, it is easier to handle than a liquid adhesive, and the operation of filling the liquid can be omitted. Therefore, the productivity is particularly excellent.

進而，若於常態、即室溫附近具備適度之接著性、例如可剝離之程度之接著性(稱作“黏性”)，則容易進行貼附時之定位，作業上非常方便，因此更佳。 Furthermore, if the adhesiveness is normal in the normal state, that is, around the room temperature, for example, the degree of releasability (referred to as "stickiness"), the positioning at the time of attachment is easy, and the operation is very convenient, so it is better. .

又，若具備進行加熱便熔融或流動之熱熔性，則可藉由進行加熱使其軟化或流動化，而追隨印刷階差等凹凸部地填充黏著劑，因此，可不產生發泡等地進行填充。 In addition, if it has the hot-melt property that melts or flows when heated, it can be softened or fluidized by heating, and the adhesive can be filled in accordance with the unevenness such as the printing step, so that it can be performed without foaming or the like. filling.

進而，若具有光交聯性，則可藉由最終使其光交聯而牢固地接著。 Furthermore, if it has photocrosslinkability, it can be firmly adhered by finally photocrosslinking it.

本黏著片材特佳為具有加熱至60℃~100℃便軟化或流動化之熱熔性者。 The adhesive sheet is particularly preferably one having a hot-melt property which is softened or fluidized when heated to 60 ° C to 100 ° C.

若具有此種熱熔性，則於常態下可保持形狀，因此，於常態下之貼合前之狀態下，保管穩定性或切斷等處理之操作性優異。 With such hot-melt properties, the shape can be maintained in the normal state. Therefore, in the state before bonding in the normal state, it has excellent storage stability and handling properties such as cutting.

又，於若不加熱至高於100℃之高溫則不軟化時，有圖像顯示裝置構成用構件因超過100℃之加熱而損傷之可能性，因此，亦可防止圖像顯示裝置構成用構件之熱損傷。 In addition, if it is not softened if it is not heated to a high temperature higher than 100 ° C, there is a possibility that the member for constituting the image display device may be damaged by heating exceeding 100 ° C. Therefore, the member for constituting the image display device may be prevented. Thermal damage.

因此，就此種觀點而言，本黏著片材較佳為具有加熱至60~100℃便軟化或流動化之熱熔性，其中，特佳為具有加熱至63℃以上或98℃以下、其中尤其是65℃以上或95℃以下便軟化或流動化之熱熔性。 Therefore, from this point of view, the present adhesive sheet preferably has a hot-melt property that softens or fluidizes when heated to 60 to 100 ° C. Among them, it is particularly preferable to have a temperature of 63 ° C or higher or 98 ° C or lower, among which It is a hot-melt that softens or flows when it is above 65 ° C or below 95 ° C.

本黏著片材既可為單層，亦可為多層。 The adhesive sheet can be a single layer or multiple layers.

於本黏著片材為多層之情形時，較佳為整體具有上述性質之黏著片材，即，於常態下可保持片狀，具有於未交聯狀態下進行加熱便熔融或流動之熱熔性，且具有可進行光交聯之光交聯性。 In the case where the adhesive sheet is multi-layered, it is preferably an adhesive sheet having the above-mentioned properties as a whole, that is, it can maintain a sheet shape in a normal state, and has a hot-melt property that melts or flows when heated in an uncrosslinked state. , And has photo-crosslinking properties that can be photo-crosslinked.

本黏著片材之厚度較佳為50μm~1mm，其中，更佳為75μm以上或500μm以下。 The thickness of the adhesive sheet is preferably 50 μm to 1 mm, and more preferably 75 μm or more or 500 μm or less.

若本黏著片材之厚度為50μm以上，則就可追隨高印刷階差等凹凸部之方面而言較佳。另一方面，若片材厚度為1mm以下，則可響應光學裝置等之薄化之要求。 If the thickness of this adhesive sheet is 50 micrometers or more, it is preferable from the point which can follow uneven | corrugated parts, such as a high printing step. On the other hand, if the sheet thickness is 1 mm or less, it can respond to the request for thinning of optical devices and the like.

進而，就甚至填埋先前之圖像顯示裝置中之周緣之隱蔽層之印刷高度更高、具體而言為80μm左右之階差的觀點而言，本黏著片材之厚度更佳為75μm以上，尤其，進而較佳為100μm以上。另一方面，就響應薄化之要求之觀點而言，較佳為500μm以下，尤其，進而較佳為350μm以下。 Furthermore, from the viewpoint that the printing height of the concealed layer on the periphery of the previous image display device is even higher, specifically, a step difference of about 80 μm, the thickness of this adhesive sheet is more preferably 75 μm or more, In particular, it is more preferably 100 μm or more. On the other hand, from the viewpoint of responding to the request for thinning, the thickness is preferably 500 μm or less, and particularly preferably 350 μm or less.

本黏著片材較佳為於交聯前之狀態下滿足下述(1)及(2)。 The present adhesive sheet preferably satisfies the following (1) and (2) in a state before crosslinking.

(1)於依據JIS-Z-0237對包含交聯前之上述透明黏著材之厚度150μm之片材進行之保持力測定中，相對於SUS(不鏽鋼)板之溫度40℃下之偏移長度未達5mm。 (1) In the measurement of the holding force of a 150 μm-thick sheet including the above-mentioned transparent adhesive material before crosslinking according to JIS-Z-0237, the offset length at 40 ° C relative to the temperature of a SUS (stainless steel) plate was not measured. Up to 5mm.

(2)於依據JIS-Z-0237對包含交聯前之上述透明黏著材之厚度150μm之片材進行之保持力測定中，相對於SUS板之溫度80℃下之偏移長度為10mm以上。 (2) In the measurement of the holding force of a 150 μm-thick sheet including the above-mentioned transparent adhesive material before crosslinking according to JIS-Z-0237, the offset length at a temperature of 80 ° C. with respect to the SUS board was 10 mm or more.

若如上述(1)般於交聯前之狀態下溫度40℃下之偏移長度未達5mm，則於加熱前之常態下，可發揮優異之形狀穩定性或加工適性。 If the offset length at a temperature of 40 ° C in the state before crosslinking is not more than 5 mm as in (1) above, in the normal state before heating, excellent shape stability or processability can be exhibited.

又，若如上述(2)般於交聯前之狀態下溫度80℃下之偏移長度為10mm以上，則不僅於例如2~4英吋之尺寸相對較小之積層體中，且於例如7英吋以上之尺寸相對較大之積層體中亦可藉由加熱至60℃~100℃而容易地將貼合之構件分離。 In addition, if the offset length at a temperature of 80 ° C in the state before crosslinking as described in (2) above is 10 mm or more, it is not only in a laminate having a relatively small size of 2 to 4 inches, but also in, for example, Laminates with a relatively large size of 7 inches or more can also be easily separated by heating to 60 ° C to 100 ° C.

本黏著片材較佳為於交聯前之狀態下滿足下述(3)及(4)。 The present adhesive sheet preferably satisfies the following (3) and (4) in a state before crosslinking.

(3)將包含交聯前之上述透明黏著材之厚度150μm之黏著片材重疊於鈉鈣玻璃，使2kg之輥往返1次進行輥壓接後，立即於23℃下以剝離角180°、剝離速度60mm/分鐘自鈉鈣玻璃將上述黏著片材剝離時之180°剝離力為5N/cm以上。 (3) An adhesive sheet having a thickness of 150 μm including the above-mentioned transparent adhesive material before crosslinking is superimposed on the soda-lime glass, and a 2 kg roller is reciprocated once to perform roll bonding, and immediately at 23 ° C. at a peel angle of 180 °, The peeling speed at 60 mm / minute when peeling the above-mentioned adhesive sheet from the soda lime glass was 180 N / cm or more.

(4)將包含交聯前之上述透明黏著材之厚度150μm之黏著片材重疊於鈉鈣玻璃，使2kg之輥往返1次進行輥壓接後，立即於85℃下以剝離角180°、剝離速度60mm/分鐘自鈉鈣玻璃將上述黏著片材剝離時之180°剝離力未達2N/cm。 (4) An adhesive sheet having a thickness of 150 μm including the above-mentioned transparent adhesive material before crosslinking is superimposed on the soda-lime glass, and a roller of 2 kg is reciprocated once for roll bonding, and then immediately peeled at 85 ° C at a peel angle of 180 °, When the peeling speed was 60 mm / minute, the 180 ° peeling force when the above-mentioned adhesive sheet was peeled from the soda lime glass did not reach 2 N / cm.

若如上述(3)般於交聯前之狀態下溫度23℃下之180°剝離力為5N/cm以上，則於通常狀態、即室溫狀態下，可表現出能剝離之程度之接著性(稱作“黏性”)，若具備此種黏性，則容易進行貼合時之定位，作業上非常方便。 If the 180 ° peeling force at a temperature of 23 ° C. in a state before crosslinking as described in (3) above is 5 N / cm or more, the adhesiveness to the extent that it can be peeled off is displayed in a normal state, that is, a room temperature state. (Referred to as "stickiness"), if such stickiness is provided, positioning at the time of bonding is easy, and operation is very convenient.

又，若如上述(4)般於交聯前之狀態下溫度85℃下之180°剝離力未達2N，則可對貼合後之構件賦予加熱時之優異之再剝離性。 In addition, if the 180 ° peeling force at a temperature of 85 ° C in a state before crosslinking as in the above (4) is less than 2N, excellent re-peelability can be imparted to the member after bonding when heated.

本黏著片材較佳為於交聯後滿足下述(5)及(6)。 The present adhesive sheet preferably satisfies the following (5) and (6) after crosslinking.

(5)將包含交聯前之上述透明黏著材之厚度150μm之黏著片材重 疊於鈉鈣玻璃，使2kg之輥往返1次進行輥壓接後，對上述透明黏著劑層以波長365nm之光達到2000mJ/cm2之方式照射光而使上述透明黏著材交聯，於該狀態下，於溫度23℃下以剝離角180°、剝離速度60mm/分鐘自鈉鈣玻璃將上述黏著片材剝離時之180°剝離力為5N/cm以上。 (5) Overlap the adhesive sheet including the above-mentioned transparent adhesive material with a thickness of 150 μm before cross-linking on the soda-lime glass, make a 2 kg roller reciprocate once, and then roll-contact the transparent adhesive layer with a wavelength of 365 nm. The transparent adhesive material was cross-linked by irradiating light at a rate of 2000 mJ / cm 2. In this state, when the adhesive sheet was peeled from the soda-lime glass at a temperature of 23 ° C. at a peel angle of 180 ° and a peel speed of 60 mm / min. The 180 ° peeling force is 5 N / cm or more.

(6)將包含交聯前之上述透明黏著材之厚度150μm之黏著片材重疊於鈉鈣玻璃，使2kg之輥往返1次進行輥壓接後，對上述透明黏著劑層以波長365nm之光達到2000mJ/cm2之方式照射光而使上述透明黏著材交聯，於該狀態下，於溫度85℃下以剝離角180°、剝離速度60mm/分鐘自鈉鈣玻璃將上述黏著片材剝離時之180°剝離力為5N/cm以上。 (6) An adhesive sheet having a thickness of 150 μm including the above-mentioned transparent adhesive material before crosslinking is superimposed on the soda-lime glass, and a 2 kg roller is reciprocated once to perform roll bonding. The transparent adhesive material was cross-linked by irradiating light at a rate of 2000 mJ / cm 2. In this state, the adhesive sheet was peeled from the soda-lime glass at a temperature of 85 ° C. at a peel angle of 180 ° and a peel speed of 60 mm / min. The 180 ° peeling force is 5 N / cm or more.

若如上述(5)般於交聯後之狀態下溫度23℃下之180°剝離力為5N/cm以上，則就可確保貼合成之積層體之常態下之對於剝離等之可靠性而言較佳。 If the 180 ° peel force at a temperature of 23 ° C. in the state after crosslinking as described in (5) above is 5 N / cm or more, the reliability of peeling and the like of the laminated body in a normal state can be ensured. Better.

又，若如上述(6)般於交聯後之狀態下溫度83℃下之180°剝離力為5N/cm以上，則可製成耐久性優異之積層體。 In addition, if the 180 ° peel force at a temperature of 83 ° C in the state after crosslinking as described in (6) above is 5 N / cm or more, a laminated body having excellent durability can be obtained.

<黏著劑組合物> <Adhesive composition>

下文將對用於形成本黏著片材之黏著劑組合物之較佳例、以及較佳之熱塑性樹脂(A)及交聯劑(B)進行敍述。此處，首先，對光聚合起始劑(C)及波長轉換劑(D)進行說明。 Hereinafter, preferred examples of the adhesive composition for forming the adhesive sheet, and preferred thermoplastic resins (A) and crosslinking agents (B) will be described. Here, first, the photopolymerization initiator (C) and the wavelength conversion agent (D) will be described.

(光聚合起始劑(C)) (Photopolymerization initiator (C))

光聚合起始劑(C)只要為藉由至少波長380nm~430nm之光線之照射，產生自由基而成為基礎樹脂之聚合反應之起點者即可。 The photopolymerization initiator (C) is only required to be a starting point of the polymerization reaction of the base resin by generating free radicals by irradiation with light having a wavelength of at least 380 nm to 430 nm.

再者，「藉由波長380nm~430nm之光而反應」之含義為只要藉由具有波長380nm~430nm之範圍之任一波長之光而反應即可，且允許藉由其他區域之波長之光而反應。概念性而言，意指若藉由具有可見光區域之波長之光而反應，則亦可藉由紫外線而反應。 In addition, the meaning of "reacting with light having a wavelength of 380nm to 430nm" means that it only needs to react with light having any wavelength in a range of 380nm to 430nm, and allows light to be emitted by light having a wavelength in other regions. reaction. Conceptually, it means that if it reacts with light having a wavelength in the visible region, it can also react with ultraviolet rays.

再者，光聚合起始劑之反應性自由基產生機制分為兩大類，分為 將自身之共價鍵裂解並分解而產生自由基之裂解型、及自系統中之氫供與體奪氫使其激發而產生自由基之奪氫型。 Furthermore, the reactive radical generation mechanisms of photopolymerization initiators are divided into two categories, divided into A cleavage type that cleaves and decomposes its own covalent bond to generate a free radical, and a hydrogen abstraction type that extracts hydrogen from a hydrogen donor in the system and excites it.

作為光聚合起始劑(C)，可為其中之任一種，尤佳為裂解型。 As the photopolymerization initiator (C), any of them may be used, and a cracking type is particularly preferred.

裂解型係於藉由光照射而產生自由基時進行分解而成為另一種化合物，若被激發一次，則喪失作為反應起始劑之功能。因此，若使用該裂解型作為藉由380nm~430nm之波長之光而反應之光聚合起始劑(C)，則與使用奪氫型之情形相比，對黏著片材實施光照射後，該光聚合起始劑(C)成為反應分解物，藉此，380nm~430nm區域之吸收消失，照射光更容易到達黏著片材之深部。因此，作為光聚合起始劑(C)，較佳為使用裂解型之光聚合起始劑。 The cleavage type is decomposed into another compound when free radicals are generated by light irradiation. If it is excited once, it loses its function as a reaction initiator. Therefore, if this cleavage type is used as a photopolymerization initiator (C) that reacts with light having a wavelength of 380 nm to 430 nm, compared with the case where a hydrogen abstraction type is used, the adhesive sheet is subjected to light irradiation. The photopolymerization initiator (C) becomes a reaction decomposition product, whereby the absorption in the region of 380 nm to 430 nm disappears, and the irradiation light more easily reaches the deep part of the adhesive sheet. Therefore, as the photopolymerization initiator (C), a cleavage-type photopolymerization initiator is preferably used.

作為光聚合起始劑(C)，例如可列舉2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)丁烷-1-酮、2-(4-甲基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)丁烷-1-酮、雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)苯基)鈦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦、9-氧硫、2-氯9-氧硫、3-甲基9-氧硫、2,4-二甲基9-氧硫、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌、1,2-辛二酮，1-(4-(苯硫基),2-(鄰苯甲醯基肟))等。該等既可使用該等中之任一種或其衍生物，又，亦可組合該等中之兩種以上而使用。 Examples of the photopolymerization initiator (C) include 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butane-1-one and 2- (4-methyl Benzyl) -2-dimethylamino-1- (4-morpholinylphenyl) butane-1-one, bis (η5-2,4-cyclopentadien-1-yl) -bis (2 , 6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, 2,4,6- Trimethylbenzyl diphenylphosphine oxide, 9-oxysulfur , 2-chloro9-oxysulfur 3-methyl 9-oxysulfur 2,4-dimethyl 9-oxosulfur , 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 1,2-octanedione, 1- (4- (phenylthio), 2- (o-benzylideneoxime)) and the like. These may use any one of them or a derivative thereof, or may use two or more of them in combination.

其中，就為裂解型光聚合性起始劑，於反應後成為分解物而消色之觀點而言，較佳為雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦。 Among these, bis (2,4,6-trimethylbenzylidene) -phenyl oxidation is preferred from the viewpoint of being a cleavage type photopolymerizable initiator and becoming a decomposed substance after the reaction to decolorize it. Phosphine, 2,4,6-trimethylbenzylidene diphenylphosphine oxide.

為調整光聚合起始劑(C)之反應性，亦可併用增感劑。 In order to adjust the reactivity of the photopolymerization initiator (C), a sensitizer may be used in combination.

作為增感劑，例如可列舉各種胺類或蒽醌、9-氧硫等化合物。其中，就於黏著組合物中之溶解性優異，不阻礙紫外線透過性之方面而言，較佳為胺系之增感劑。 Examples of the sensitizer include various amines, anthraquinones, and 9-oxosulfur. And other compounds. Among them, an amine-based sensitizer is preferred because it has excellent solubility in the adhesive composition and does not hinder ultraviolet light transmission.

(波長轉換劑(D)) (Wavelength conversion agent (D))

波長轉換劑(D)較佳為被較波長380nm為短波長側之光激發而發出至少波長380nm~550nm之光者。 The wavelength conversion agent (D) is preferably one which is excited by light having a shorter wavelength side than a wavelength of 380 nm and emits light having a wavelength of at least 380 nm to 550 nm.

只要被較波長380nm為短波長側之光激發即可，其中，較佳為包含較波長370nm為短波長側之光作為激發區域者。 It is only necessary to be excited by light having a shorter wavelength side than a wavelength of 380 nm, and among them, it is preferable to include light having a shorter wavelength side than a wavelength of 370 nm as an excitation region.

又，只要發出至少波長380nm~550nm中之任一波長域之光即可，其中，較佳為包含波長390nm~500nm作為發光區域者。 In addition, it is only necessary to emit light in any one of wavelength ranges of 380 nm to 550 nm, and among them, it is preferable to include a wavelength of 390 nm to 500 nm as a light emitting region.

就該觀點而言，作為較佳之波長轉換劑(D)，例如可列舉唑系螢光體、***系螢光體、噻吩系螢光等，可使用該等中之一種，或組合該等中之兩種以上而使用。 From this viewpoint, examples of the preferable wavelength conversion agent (D) include: An azole-based fluorescent substance, a triazole-based fluorescent substance, a thiophene-based fluorescent substance, or the like may be used alone or in combination of two or more of them.

波長轉換劑(D)較佳為相溶於熱塑性樹脂(A)之材料。若波長轉換劑(D)為相溶於熱塑性樹脂(A)之材料，則可進一步提高透明。 The wavelength conversion agent (D) is preferably a material compatible with the thermoplastic resin (A). If the wavelength conversion agent (D) is a material compatible with the thermoplastic resin (A), the transparency can be further improved.

就該觀點而言，較佳為有機系之螢光體。 From this viewpoint, an organic phosphor is preferable.

(波長轉換劑(D)之濃度) (Concentration of wavelength conversion agent (D))

若波長轉換劑(D)之濃度過濃，則有交聯用之光被波長轉換劑(D)阻斷而未到達黏著片材之深部之情形。又，即便波長轉換劑(D)之濃度較低，於黏著片材之厚度較大之情形時，亦有光仍未到達黏著片材之深部之情形。 If the concentration of the wavelength conversion agent (D) is too high, the light for cross-linking may be blocked by the wavelength conversion agent (D) and may not reach the deep part of the adhesive sheet. In addition, even if the concentration of the wavelength conversion agent (D) is low, when the thickness of the adhesive sheet is large, light may not reach the deep part of the adhesive sheet.

因此，於本黏著片材中，較佳為以黏著片材之波長390nm下之吸光度X與黏著片材之厚度Y滿足下述關係式(1)之方式調整波長轉換劑(D)之濃度及黏著片材之厚度等。 Therefore, in this adhesive sheet, it is preferable to adjust the concentration of the wavelength conversion agent (D) in such a manner that the absorbance X and the thickness Y of the adhesive sheet at a wavelength of 390 nm of the adhesive sheet satisfy the following relational expression (1) and Thickness of adhesive sheet, etc.

式(1)...0.5≦X/Y≦12 Equation (1) ... 0.5 ≦ X / Y ≦ 12

其中，進而較佳為以滿足式(2)之方式進行調整。 Among these, it is more preferable to adjust it so as to satisfy the formula (2).

式(2)...0.7≦X/Y≦11 Equation (2) ... 0.7 ≦ X / Y ≦ 11

進而，其中，進而較佳為以滿足式(3)之方式進行調整。 Furthermore, among these, it is more preferable to adjust so as to satisfy the formula (3).

式(3)...0.9≦X/Y≦10 Equation (3) ... 0.9 ≦ X / Y ≦ 10

又，就上述同樣之觀點而言，較佳為以本黏著片材之波長390nm之透過率成為3~95%、其中成為5%以上或85%以下、且其中成為7%以上或80%以下之範圍內之方式調整波長轉換劑(D)之濃度。 From the same viewpoint as described above, it is preferable that the transmittance at a wavelength of 390 nm of the present adhesive sheet is 3 to 95%, of which 5% or more or 85% or less, and 7% or more or 80% or less thereof. The concentration of the wavelength conversion agent (D) is adjusted in a manner within the range.

<帶有剝離膜之黏著片材> <Adhesive sheet with release film>

本黏著片材亦可為於正背面一側或兩側具備剝離膜之帶有剝離膜之黏著片材。 The adhesive sheet may also be an adhesive sheet with a release film having a release film on one or both sides of the front and back surfaces.

此時，關於用於本黏著片材之剝離膜，特佳為至少正背面一側之剝離膜係較波長380nm為短波長側之光之光線透過率為40%以下、其中為35%以下、且其中為30%以下之膜。 At this time, as for the release film used for this adhesive sheet, it is particularly preferable that the release film on at least the front and back sides has a light transmittance of 40% or less, of which the light transmittance is shorter than the wavelength of 380nm, of which 35% or less, Among them, the film is 30% or less.

若剝離膜係較波長380nm為短波長側之光之光線透過率為40%以下之膜，則可某程度上阻斷與反應開始相關之光，因此，例如於保存狀態下，可抑制光聚合起始劑(C)之反應開始，並且可抑制波長轉換劑(D)之激發。 If the release film is a film having a light transmittance of 40% or less on the short-wavelength side of the light at a wavelength of 380 nm, the light related to the start of the reaction can be blocked to a certain extent. Therefore, for example, in a storage state, photopolymerization can be suppressed. The reaction of the initiator (C) starts, and the excitation of the wavelength conversion agent (D) can be suppressed.

作為較波長380nm為短波長側之光之光線透過率為40%以下之剝離膜，例如可列舉含有紫外線吸收劑之膜、將紫外線吸收劑塗佈或印刷於表面而成之膜、積層含有紫外線吸收劑之層而成之膜、紙製之剝離膜等。 Examples of the peeling film having a light transmittance of 40% or less on the short-wavelength side of the wavelength of 380 nm include a film containing an ultraviolet absorbent, a film obtained by coating or printing an ultraviolet absorbent on a surface, and a laminate containing ultraviolet rays. Films made of absorbent layers, release films made of paper, etc.

<用途> <Use>

本黏著片材可較佳地用於貼合例如構成圖像顯示裝置之圖像顯示裝置構成用構件。但，本黏著片材之用途不限定於此種用途。 This adhesive sheet can be used suitably for bonding the components for image display apparatuses which comprise an image display apparatus, for example. However, the application of the present adhesive sheet is not limited to such applications.

作為該圖像顯示裝置，例如可列舉個人電腦、個人數位助理(PDA)、遊戲機、電視(TV)、汽車導航、觸控面板、手寫板等。但，不限定於該等。 Examples of the image display device include a personal computer, a personal digital assistant (PDA), a game machine, a television (TV), a car navigation system, a touch panel, and a tablet. However, it is not limited to these.

又，作為圖像顯示裝置構成用構件之具體例，例如可列舉觸控面板、圖像顯示面板、表面保護面板、相位差膜、偏光膜等，既可為該等中之任一者，亦可為已積層有該等中之2種以上之積層體。但，不限 定於該等。 In addition, as specific examples of the components of the image display device, for example, a touch panel, an image display panel, a surface protection panel, a retardation film, a polarizing film, and the like may be mentioned. It may be a laminated body in which two or more of these are laminated. But not limited Scheduled.

<本黏著劑組合物> <This adhesive composition>

作為上述本黏著劑組合物之較佳例，對黏著劑組合物(I)、(II)進行說明。但，本黏著劑組合物不限定於下述黏著劑組合物(I)、(II)。 As a preferable example of the said adhesive composition, the adhesive composition (I) and (II) are demonstrated. However, the present adhesive composition is not limited to the following adhesive compositions (I) and (II).

再者，於將本黏著片材設為多層之片材之情形時，最外層較佳為與上述單層之情形同樣地兼具凹凸追隨性及耐發泡可靠性，因此，較佳為使用黏著劑組合物、例如黏著劑組合物(1)、(II)而形成。 Furthermore, when the present adhesive sheet is a multilayer sheet, the outermost layer is preferably the same as the case of the above-mentioned single layer, and has both unevenness followability and foaming reliability. Therefore, it is preferably used. An adhesive composition, for example, the adhesive composition (1), (II) is formed.

另一方面，中間層由於無助於與圖像顯示裝置構成構件之黏著，故而較佳為具有無損透明性且不阻礙最外層之2次硬化反應之程度之光透過性，且具有提高切割性及操作性之性質。 On the other hand, since the intermediate layer does not contribute to the adhesion to the constituent elements of the image display device, it is preferred that it has light transmittance to the extent that it does not impair transparency and does not hinder the secondary curing reaction of the outermost layer, and has improved cutting properties. And operational properties.

關於形成中間層之基礎聚合物之種類，只要為透明樹脂，則無特別限定。形成中間層之基礎聚合物既可為與最外層之基礎聚合物相同之樹脂，亦可為不同之樹脂。其中，就透明性確保或製作容易度、進而防止積層邊界面處之光之折射之觀點而言，較佳為使用與最外層之基礎聚合物相同之丙烯酸系樹脂。 The type of the base polymer forming the intermediate layer is not particularly limited as long as it is a transparent resin. The base polymer forming the intermediate layer may be the same resin as the outermost base polymer or a different resin. Among these, from the viewpoint of ensuring transparency or ease of production and preventing refraction of light at the boundary surface of the laminate, it is preferable to use the same acrylic resin as the outermost base polymer.

中間層及其他樹脂層既可具有活性能量線硬化性，亦可不具。既可以藉由例如紫外線交聯而硬化之方式形成，亦可以藉由熱而硬化之方式形成。又，亦可以不特別進行後硬化之方式形成。但，若考慮與最外層之密接性等，則較佳為以進行後硬化之方式形成，尤佳為以進行紫外線交聯之方式形成。 The intermediate layer and other resin layers may or may not have active energy ray hardening properties. It can be formed by, for example, curing by ultraviolet cross-linking or by curing by heat. In addition, it may be formed without performing post-curing in particular. However, in consideration of the adhesion to the outermost layer, etc., it is preferably formed by performing post-hardening, and particularly preferably formed by performing ultraviolet crosslinking.

此時，若交聯起始劑之含量變多，則光透過率降低，因此，較佳為以中間層中之交聯起始劑較外層中之含有率低之含有率包含紫外線交聯劑。 At this time, if the content of the cross-linking initiator increases, the light transmittance decreases. Therefore, it is preferable to include an ultraviolet cross-linking agent at a lower content of the cross-linking initiator in the intermediate layer than in the outer layer. .

於將本黏著片材設為多層之黏著片材之情形時，作為積層構成，具體而言，例如可列舉積層黏著劑組合物(I)、(II)、及其他黏著劑組合物而成之2種2層構成、或隔著中間樹脂層於正背面配置黏著劑組合物 (I)、(II)而成之2種3層構成、或依序積層黏著劑組合物(I)、(II)、中間樹脂組合物、及其他黏著劑組合物而成之3種3層構成等。 In the case where the present adhesive sheet is a multilayer adhesive sheet, as the laminated structure, specifically, for example, laminated adhesive compositions (I), (II), and other adhesive compositions are used. Two types of two-layer structure, or an adhesive composition disposed on the front and back sides with an intermediate resin layer interposed therebetween (I), (II), two types of three-layer structure, or three layers of three types of adhesive composition (I), (II), intermediate resin composition, and other adhesive composition Composition etc.

<黏著劑組合物(I)> <Adhesive composition (I)>

作為黏著劑組合物(I)，可列舉如下之樹脂組合物，其含有包含具備巨單體作為分支成分之接枝共聚物之丙烯酸系共聚物(A1)、交聯劑(B1)、光聚合起始劑(C1)、及波長轉換劑(D1)。 Examples of the adhesive composition (I) include a resin composition containing an acrylic copolymer (A1) containing a graft copolymer having a macromonomer as a branching component, a crosslinking agent (B1), and photopolymerization. An initiator (C1) and a wavelength conversion agent (D1).

(丙烯酸系共聚物(A1)) (Acrylic copolymer (A1))

上述丙烯酸系共聚物(A1)只要為具備巨單體作為分支成分之接枝共聚物即可。 The acrylic copolymer (A1) may be a graft copolymer having a macromonomer as a branching component.

(主幹成分) (Stem component)

上述丙烯酸系共聚物(A1)之主幹成分較佳為包含含有源自(甲基)丙烯酸酯之重複單元之共聚物成分。 The backbone component of the acrylic copolymer (A1) is preferably a copolymer component containing a repeating unit derived from a (meth) acrylate.

構成上述丙烯酸系共聚物(A1)之主幹成分之共聚物之玻璃轉移溫度較佳為-70~0℃。 The glass transition temperature of the copolymer constituting the main component of the acrylic copolymer (A1) is preferably -70 to 0 ° C.

此時，所謂構成主幹成分之共聚物成分之玻璃轉移溫度係指僅使組成丙烯酸系共聚物(A1)之主幹成分之單體成分共聚合而獲得之聚合物之玻璃轉移溫度。具體而言，意指藉由Fox之計算式，根據由該共聚物各成分之均聚物而獲得之聚合物之玻璃轉移溫度與構成比率所算出之值。 At this time, the glass transition temperature of the copolymer component constituting the backbone component refers to the glass transition temperature of the polymer obtained by copolymerizing only the monomer components constituting the backbone component of the acrylic copolymer (A1). Specifically, it means the value calculated from the glass transition temperature and composition ratio of the polymer obtained from the homopolymer of each component of this copolymer by the calculation formula of Fox.

再者，所謂Fox之計算式係指藉由以下之式而求出之計算值，可使用聚合物手冊[Polymer HandBook，J.Brandrup，Interscience，1989]中所記載之值而求出。 In addition, the calculation formula of Fox means the calculation value calculated | required by the following formula, and can be calculated | required using the value described in a polymer manual [Polymer HandBook, J. Brandrup, Interscience, 1989].

1/(273+Tg)=Σ(Wi/(273+Tgi)) 1 / (273 + Tg) = Σ (Wi / (273 + Tgi))

[式中，Wi表示單體i之重量分率，Tgi表示單體i之均聚物之Tg(℃)] [In the formula, Wi represents the weight fraction of monomer i, and Tgi represents the Tg (° C) of the homopolymer of monomer i]

由於構成上述丙烯酸系共聚物(A1)之主幹成分之共聚物成分之玻璃轉移溫度會影響室溫狀態下之黏著劑組合物(I)之柔軟性、或黏著劑 組合物(I)對被黏著體之潤濕性、即接著性，故而為使黏著劑組合物(I)於室溫狀態下獲得適度之接著性(黏性)，該玻璃轉移溫度較佳為-70℃~0℃，其中尤佳為-65℃以上或-5℃以下，且其中為-60℃以上或-10℃以下。 The glass transition temperature of the copolymer component constituting the main component of the acrylic copolymer (A1) affects the flexibility of the adhesive composition (I) or the adhesive at room temperature. Since the composition (I) has wettability, that is, adhesion, to the adherend, the glass transition temperature is preferably in order that the adhesive composition (I) can obtain moderate adhesion (tackiness) at room temperature. -70 ° C to 0 ° C, in which -65 ° C or more or -5 ° C or less is particularly preferable, and -60 ° C or more or -10 ° C or less is preferable.

但，即便該共聚物成分之玻璃轉移溫度為相同之溫度，亦可藉由調整分子量而調整黏彈性。例如可藉由減小共聚物成分之分子量，而使其更柔軟化。 However, even if the glass transition temperature of the copolymer component is the same temperature, the viscoelasticity can be adjusted by adjusting the molecular weight. For example, the copolymer component can be made softer by reducing the molecular weight of the copolymer component.

作為上述丙烯酸系共聚物(A1)之主幹成分所含有之(甲基)丙烯酸酯單體，例如可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山萮酯、(甲基)丙烯酸異基酯、(甲基)丙烯酸2-苯氧基乙酯、3,5,5-三甲基環己烷丙烯酸酯、對異丙苯基苯酚EO改性(甲基)丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸苄酯等。除該等以外，亦可使用具有親水基或有機官能基等之(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、甘油(甲基)丙烯酸酯等含羥基之(甲基)丙烯酸酯，或(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基鄰苯二甲酸、 2-(甲基)丙烯醯氧基乙基順丁烯二酸、2-(甲基)丙烯醯氧基丙基順丁烯二酸、2-(甲基)丙烯醯氧基乙基丁二酸、2-(甲基)丙烯醯氧基丙基丁二酸、丁烯酸、反丁烯二酸、順丁烯二酸、亞甲基丁二酸、順丁烯二酸單甲酯、亞甲基丁二酸單甲酯等含羧基之單體，順丁烯二酸酐、亞甲基丁二酸酐等含酸酐基之單體，(甲基)丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧丁酯等含環氧基之單體，(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯等含胺基之(甲基)丙烯酸酯系單體，(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、二丙酮(甲基)丙烯醯胺、順丁烯二醯胺、順丁烯二醯亞胺等含有醯胺基之單體，乙烯基吡咯啶酮、乙烯基吡啶、乙烯基咔唑等雜環系鹼性單體等。 Examples of the (meth) acrylate monomer contained in the main component of the acrylic copolymer (A1) include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, (a Base) amyl acrylate, isoamyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, ( 2-ethylhexyl methacrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, (meth) Third butyl cyclohexyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid Cetyl ester, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, (iso) methacrylate Ester, 2-phenoxyethyl (meth) acrylate, 3,5,5-trimethylcyclohexane acrylate, p-cumylphenol EO modified (meth) acrylate, (meth) ) Dicyclopentyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, and the like. In addition to these, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycerol (meth) acrylic acid having a hydrophilic group or an organic functional group, etc. may be used. (Meth) acrylic acid esters containing hydroxyl groups, or (meth) acrylic acid, 2- (meth) acryloxyethylhexahydrophthalic acid, 2- (meth) acryloxypropyl Hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalate, 2- (meth) acryloxypropyl phthalate, 2- (meth) acryloxy Ethyl maleic acid, 2- (meth) acryloxypropyl maleic acid, 2- (meth) acryl ethyl ethyl succinic acid, 2- (meth) acrylic acid Methoxypropylsuccinic acid, butenoic acid, fumaric acid, maleic acid, methylene succinic acid, maleic acid monomethyl ester, methylene succinic acid monomethyl ester Monomers containing carboxyl groups, monomers containing anhydride groups such as maleic anhydride, methylene succinic anhydride, glycidyl (meth) acrylate, glycidyl α-ethylacrylate, (meth) acrylic acid Epoxy group-containing monomers such as 3,4-butylene oxide, (methyl) (Meth) acrylic acid ester-based monomers such as dimethylaminoethyl acrylate and diethylaminoethyl (meth) acrylate, (meth) acrylamidonium, N-third butyl (methyl Acrylamide, N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diamine Acetyl (meth) acrylamide, maleimide, and maleimide-containing monomers, such as vinylpyrrolidone, vinylpyridine, vinylcarbazole, and other heterocyclic systems Basic monomers, etc.

又，亦可適當地使用可與上述丙烯酸系單體或甲基丙烯酸系單體共聚合之苯乙烯、第三丁基苯乙烯、α-甲基苯乙烯、乙烯基甲苯、丙烯腈、甲基丙烯腈、乙酸乙烯酯、丙酸乙烯酯、烷基乙烯基醚、羥基烷基乙烯基醚、烷基乙烯基單體等各種乙烯基單體。 Also, styrene, third butylstyrene, α-methylstyrene, vinyltoluene, acrylonitrile, and methyl which can be copolymerized with the acrylic monomer or methacrylic monomer can be used as appropriate. Various vinyl monomers, such as acrylonitrile, vinyl acetate, vinyl propionate, alkyl vinyl ether, hydroxyalkyl vinyl ether, and alkyl vinyl monomer.

又，丙烯酸系共聚物(A1)之主幹成分較佳為含有疏水性之(甲基)丙烯酸酯單體、及親水性之(甲基)丙烯酸酯單體作為結構單元。 The backbone component of the acrylic copolymer (A1) preferably contains a hydrophobic (meth) acrylate monomer and a hydrophilic (meth) acrylate monomer as structural units.

若丙烯酸系共聚物(A1)之主幹成分僅由疏水性單體構成，則確認有濕熱白化之傾向，因此，較佳為亦將親水性單體導入主幹成分而防止濕熱白化。 When the main component of the acrylic copolymer (A1) is composed of only a hydrophobic monomer, moist-heat whitening tends to be confirmed. Therefore, it is preferable to introduce a hydrophilic monomer into the main component to prevent moist-heat whitening.

具體而言，作為上述丙烯酸系共聚物(A1)之主幹成分，可列舉疏水性之(甲基)丙烯酸酯單體、親水性之(甲基)丙烯酸酯單體、及巨單體之末端之聚合性官能基進行無規共聚而成之共聚物成分。 Specifically, as a main component of the said acrylic copolymer (A1), the hydrophobic (meth) acrylate monomer, the hydrophilic (meth) acrylate monomer, and the terminal of a macromonomer are mentioned. A copolymer component in which a polymerizable functional group is randomly copolymerized.

此處，作為上述疏水性之(甲基)丙烯酸酯單體，例如可列舉(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基) 丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山萮酯、(甲基)丙烯酸異基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊烯氧基乙酯、甲基丙烯酸甲酯。 Here, examples of the hydrophobic (meth) acrylate monomer include n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, and (meth) acrylate. Group) tert-butyl acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate , Heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, (meth) ) Isononyl acrylate, tert-butyl cyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, (meth) ) Lauryl acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, (iso) methacrylate Ester, cyclohexyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methyl methacrylate.

又，作為疏水性之乙烯基單體，可列舉乙酸乙烯酯、苯乙烯、第三丁基苯乙烯、α-甲基苯乙烯、乙烯基甲苯、烷基乙烯基單體等。 Examples of the hydrophobic vinyl monomer include vinyl acetate, styrene, third butylstyrene, α-methylstyrene, vinyl toluene, and an alkyl vinyl monomer.

作為上述親水性之(甲基)丙烯酸酯單體，例如可列舉(甲基)丙烯酸甲酯，(甲基)丙烯酸，(甲基)丙烯酸四氫呋喃甲酯，或(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、甘油(甲基)丙烯酸酯等含羥基之(甲基)丙烯酸酯，或(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基順丁烯二酸、2-(甲基)丙烯醯氧基丙基順丁烯二酸、2-(甲基)丙烯醯氧基乙基丁二酸、2-(甲基)丙烯醯氧基丙基丁二酸、丁烯酸、反丁烯二酸、順丁烯二酸、亞甲基丁二酸、順丁烯二酸單甲酯、亞甲基丁二酸單甲酯等含羧基之單體，順丁烯二酸酐、亞甲基丁二酸酐等含酸酐基之單體，(甲基)丙烯酸縮水甘油酯、α-乙基(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧丁酯等含環氧基之單體，甲氧基聚乙二醇(甲基)丙烯酸酯等烷氧基聚伸烷基二醇(甲基)丙烯酸酯，N,N-二甲基丙烯醯胺、羥基乙基丙烯醯胺等。 Examples of the hydrophilic (meth) acrylate monomer include methyl (meth) acrylate, (meth) acrylic acid, tetrahydrofuran methyl (meth) acrylate, or hydroxyethyl (meth) acrylate, Hydroxy-containing (meth) acrylates such as hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or (meth) acrylic acid, 2- (meth) acrylic acid Ethoxyethyl hexahydrophthalic acid, 2- (meth) acrylic ethoxypropyl hexahydrophthalic acid, 2- (meth) acrylic ethoxyethyl phthalic acid, 2- (Meth) acryloxypropyl phthalic acid, 2- (meth) acryloxyethyl maleic acid, 2- (meth) acryloxypropyl maleic acid , 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxypropyl succinic acid, butenoic acid, fumaric acid, maleic acid, Carboxyl-containing monomers such as methyl succinic acid, monomethyl maleate, and monomethyl methylene succinate; anhydride-containing monomers such as maleic anhydride, methylene succinic anhydride , Glycidyl (meth) acrylate, α-ethyl (methyl) Epoxy group-containing monomers, such as glycidyl acrylate, 3,4-epoxybutyl (meth) acrylate, and alkoxy polyalkylene dialkyl, such as methoxy polyethylene glycol (meth) acrylate Alcohol (meth) acrylate, N, N-dimethylacrylamide, hydroxyethylacrylamide and the like.

(分支成分：巨單體) (Branch component: macromonomer)

對於丙烯酸系共聚物(A1)，導入巨單體作為接枝共聚物之分支成分而含有源自巨單體之重複單元較為重要。 For the acrylic copolymer (A1), it is important to introduce a macromonomer as a branch component of the graft copolymer and to include a repeating unit derived from the macromonomer.

所謂巨單體係指具有末端之聚合性官能基及高分子量骨架成分之高分子單體。 The so-called macromonomer system refers to a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.

巨單體之玻璃轉移溫度(Tg)較佳為高於構成上述丙烯酸系共聚物(A1)之共聚物成分之玻璃轉移溫度。 The glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer component constituting the acrylic copolymer (A1).

具體而言，由於巨單體之玻璃轉移溫度(Tg)會影響黏著劑組合物(I)之加熱熔融溫度(熱熔溫度)，故而巨單體之玻璃轉移溫度(Tg)較佳為30℃~120℃，其中進而較佳為40℃以上或110℃以下，且其中為50℃以上或100℃以下。 Specifically, since the glass transition temperature (Tg) of the macromonomer affects the heating and melting temperature (hot melt temperature) of the adhesive composition (I), the glass transition temperature (Tg) of the macromonomer is preferably 30 ° C. ~ 120 ° C, among which it is more preferably 40 ° C or higher or 110 ° C or lower, and among them, 50 ° C or higher or 100 ° C or lower.

若為此種玻璃轉移溫度(Tg)，則藉由調整分子量，可保持優異之加工性或保管穩定性，並且可調整為於80℃附近熱熔。 If it is such a glass transition temperature (Tg), by adjusting molecular weight, excellent processability or storage stability can be maintained, and it can be adjusted to hot-melt around 80 ° C.

所謂巨單體之玻璃轉移溫度係指該巨單體本身之玻璃轉移溫度，可藉由示差掃描熱量計(DSC)進行測定。 The so-called glass transition temperature of the macromonomer refers to the glass transition temperature of the macromonomer itself, which can be measured by a differential scanning calorimeter (DSC).

又，為使得於室溫狀態下可維持分支成分彼此牽引而作為黏著劑組合物進行物理***聯般之狀態，並且可藉由加熱至適度之溫度而使上述物理***聯崩解以獲得流動性，亦較佳為調整巨單體之分子量或含量。 In addition, in order to maintain the state that the branched components are drawn to each other at room temperature, and perform physical crosslinking as an adhesive composition, the physical crosslinking can be disintegrated by heating to a moderate temperature to obtain fluidity It is also preferable to adjust the molecular weight or content of the macromonomer.

就該觀點而言，巨單體較佳為於丙烯酸系共聚物(A1)中以5質量%~30質量%之比率含有，其中較佳為6質量%以上或25質量%以下，且其中為8質量%以上或20質量%以下。 From this viewpoint, the macromonomer is preferably contained in the acrylic copolymer (A1) at a ratio of 5% to 30% by mass, and among them, it is preferably 6% by mass or more or 25% by mass, and among them 8% by mass or 20% by mass.

又，巨單體之數量平均分子量較佳為500以上且未達8000，其中較佳為800以上且未達7500，且其中為1000以上且未達7000。 The number-average molecular weight of the macromonomer is preferably 500 or more and less than 8,000, of which 800 or more and less than 7500 are preferred, and 1000 or more and less than 7,000 are more preferred.

巨單體可適當地使用通常所製造者(例如東亞合成公司製造之巨單體等)。 As the macromonomer, an ordinary manufacturer (for example, a macromonomer manufactured by Toa Synthesis Co., Ltd.) can be used as appropriate.

巨單體之高分子量骨架成分較佳為包含丙烯酸系聚合物或乙烯 系聚合物。 The macromolecular high molecular weight skeleton component preferably contains an acrylic polymer or ethylene Department of polymers.

作為上述巨單體之高分子量骨架成分，例如可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山萮酯、(甲基)丙烯酸異基酯、(甲基)丙烯酸2-苯氧基乙酯、3,5,5-三甲基環己烷(甲基)丙烯酸酯、對異丙苯基苯酚EO改性(甲基)丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸羥基烷酯、(甲基)丙烯酸、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、(甲基)丙烯腈、(甲基)丙烯酸烷氧基烷基酯、烷氧基聚伸烷基二醇(甲基)丙烯酸酯等(甲基)丙烯酸酯單體、或苯乙烯、第三丁基苯乙烯、α-甲基苯乙烯、乙烯基甲苯、烷基乙烯基單體、乙酸乙烯酯、烷基乙烯基醚、羥基烷基乙烯基醚等各種乙烯基單體，該等可單獨或組合2種以上而使用。 Examples of the high molecular weight skeleton component of the macromonomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and (methyl) ) N-butyl acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate Ester, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (formyl) N-octyl acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, (meth) Decyl acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearin (meth) acrylate Ester, isostearyl (meth) acrylate, behenyl (meth) acrylate, isoisopropyl (meth) acrylate Ester, 2-phenoxyethyl (meth) acrylate, 3,5,5-trimethylcyclohexane (meth) acrylate, p-cumylphenol EO modified (meth) acrylate , Dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, hydroxyl (meth) acrylate Alkyl esters, (meth) acrylic acid, glycidyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acrylonitrile, (formaldehyde) (Meth) acrylate (meth) acrylate monomers such as alkoxyalkyl acrylate, alkoxy polyalkylene glycol (meth) acrylate, or styrene, tertiary butyl styrene, α-methyl Various vinyl monomers such as styrene, vinyl toluene, alkyl vinyl monomer, vinyl acetate, alkyl vinyl ether, and hydroxyalkyl vinyl ether, and these can be used alone or in combination of two or more kinds.

作為上述巨單體之末端聚合性官能基，例如可列舉甲基丙烯醯基、丙烯醯基、乙烯基等。 Examples of the terminal polymerizable functional group of the macromonomer include a methacryl group, an acryl group, and a vinyl group.

(丙烯酸系共聚物(A1)之物性) (Physical properties of acrylic copolymer (A1))

上述丙烯酸系共聚物(A1)之溫度130℃、頻率0.02Hz下之複黏度較佳為100~800Pa‧s，更佳為150~700Pa‧s，進而較佳為170~600 Pa‧s。 The complex viscosity of the acrylic copolymer (A1) at a temperature of 130 ° C. and a frequency of 0.02 Hz is preferably 100 to 800 Pa · s, more preferably 150 to 700 Pa · s, and still more preferably 170 to 600. Pa‧s.

上述丙烯酸系共聚物(A1)之溫度130℃下之複黏度會影響使該透明雙面黏著材熱熔而使用時之黏著劑組合物(I)之流動性，因此，若該複黏度為100~800Pa‧s，則可具有優異之熱熔適性。 The reviscosity of the acrylic copolymer (A1) at a temperature of 130 ° C will affect the fluidity of the adhesive composition (I) when the transparent double-sided adhesive is hot-melted and used. Therefore, if the reviscosity is 100 ~ 800Pa‧s, can have excellent hot melt suitability.

於將上述丙烯酸系共聚物(A1)之複黏度調整為上述範圍時，例如可列舉調整丙烯酸系共聚物(A1)之重量平均分子量、或構成丙烯酸系共聚物(A1)之主幹成分之共聚物成分之玻璃轉移溫度。 When the complex viscosity of the acrylic copolymer (A1) is adjusted to the above range, for example, a copolymer that adjusts the weight average molecular weight of the acrylic copolymer (A1) or the backbone component constituting the acrylic copolymer (A1) can be mentioned. The glass transition temperature of the ingredients.

作為丙烯酸系共聚物(A1)之重量平均分子量，較佳為5萬~50萬，其中，較佳為12萬以上或45萬以下，其中，更佳為15萬以上或40萬以下。 The weight average molecular weight of the acrylic copolymer (A1) is preferably 50,000 to 500,000, of which 120,000 or more or 450,000 or less is preferable, and 150,000 or more or 400,000 or less is more preferable.

又，可列舉如下方法：作為構成丙烯酸系共聚物(A1)之主幹成分之共聚物成分之玻璃轉移溫度，較佳為調整為-70℃~0℃、其中為-65℃以上或-5℃以下、且其中為-60℃以上或-10℃以下，並且調整該共聚物成分之分子量而調整黏彈性。但，不限定於該方法。 In addition, the following method can be mentioned: The glass transition temperature of the copolymer component constituting the backbone component of the acrylic copolymer (A1) is preferably adjusted to -70 ° C to 0 ° C, of which -65 ° C or higher or -5 ° C. Below, and in which, it is -60 ° C or higher or -10 ° C or lower, and the molecular weight of the copolymer component is adjusted to adjust the viscoelasticity. However, it is not limited to this method.

(交聯劑(B1)) (Crosslinking agent (B1))

作為交聯劑(B1)，可適當地選擇例如環氧交聯劑或異氰酸酯交聯劑、包含氧雜環丁烷化合物、矽烷化合物、丙烯酸系化合物等之交聯劑。其中，就反應性或所獲得之硬化物之強度之方面而言，較佳為具有2個以上、其中為3個以上之(甲基)丙烯醯基之多官能(甲基)丙烯酸酯。 As the crosslinking agent (B1), for example, an epoxy crosslinking agent or an isocyanate crosslinking agent, a crosslinking agent containing an oxetane compound, a silane compound, an acrylic compound, or the like can be appropriately selected. Among these, a polyfunctional (meth) acrylate having two or more (meth) acrylfluorenyl groups is preferred in terms of reactivity or strength of the obtained hardened material.

使圖像顯示裝置構成構件貼合一體化後，使交聯劑(B1)於黏著材中交聯，藉此，該片材失去熱熔性而表現出高溫環境下之較高之凝聚力，可獲得優異之耐發泡可靠性。 After laminating and integrating the constituent components of the image display device, the cross-linking agent (B1) is cross-linked in the adhesive material, whereby the sheet loses its hot-melt property and exhibits a high cohesive force in a high-temperature environment. Obtain excellent foam resistance.

作為此種多官能(甲基)丙烯酸酯，例如可列舉1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、甘油縮水甘油醚二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬 二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、雙酚A聚乙氧基二(甲基)丙烯酸酯、雙酚A聚烷氧基二(甲基)丙烯酸酯、雙酚F聚烷氧基二(甲基)丙烯酸酯、聚伸烷基二醇二(甲基)丙烯酸酯、三羥甲基丙烷三氧基乙基(甲基)丙烯酸酯、ε-己內酯改性三(2-羥基乙基)異氰尿酸酯三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、烷氧基化季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、烷氧基化季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、烷氧基化二季戊四醇六(甲基)丙烯酸酯、聚伸烷基二醇二(甲基)丙烯酸酯、異氰尿酸三(丙烯醯氧基乙基)酯、二季戊四醇五(甲基)丙烯酸酯、烷氧基化二季戊四醇五(甲基)丙烯酸酯、三季戊四醇六(甲基)丙烯酸酯、三季戊四醇五(甲基)丙烯酸酯、羥基特戊酸新戊二醇二(甲基)丙烯酸酯、羥基特戊酸新戊二醇酯之ε-己內酯加成物之二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、烷氧基化三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯等紫外線硬化型之多官能單體類、以及聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯、聚醚(甲基)丙烯酸酯等多官能丙烯酸系低聚物類。 Examples of such a polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and glycerol di (meth) acrylate , Glycerol glycidyl ether di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonyl Glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxy di (meth) acrylate, bisphenol A polyalkoxy di (methyl) ) Acrylate, bisphenol F polyalkoxydi (meth) acrylate, polyalkylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ε-caprolactone modified tri (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, alkoxylated pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, alkoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkoxylated dipentaerythritol hexa (meth) acrylate, polyalkylene Diethylene glycol di (meth) acrylate, tris (propyleneoxyethyl) isocyanurate, dipentaerythritol penta (meth) acrylate, alkoxylated dipentaerythritol penta (meth) acrylate, tripentaerythritol Hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, neopentyl glycol di (meth) acrylate, pentopenate Di- (meth) acrylates of ε-caprolactone adducts of glycol esters, trimethylolpropane tri (meth) acrylate, alkoxylated trimethylolpropane tri (meth) acrylate , UV-curable polyfunctional monomers such as, di-trimethylolpropane tetra (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, (meth) acrylic acid Multifunctional acrylic oligomers such as urethane and polyether (meth) acrylate.

上述列舉中，就提高對被黏著體之密接性或濕熱白化抑制之效果之觀點而言，較佳為含有羥基等極性官能基之多官能單體或低聚物。 Among the above-mentioned enumerations, a polyfunctional monomer or oligomer containing a polar functional group such as a hydroxyl group is preferred from the viewpoint of improving the adhesion to the adherend or the effect of suppressing moist heat whitening.

其中，較佳為使用具有羥基之多官能(甲基)丙烯酸酯。 Among these, it is preferable to use a polyfunctional (meth) acrylate having a hydroxyl group.

因此，就防止濕熱白化之觀點而言，較佳為含有疏水性之丙烯酸酯單體、及親水性之丙烯酸酯單體作為上述丙烯酸系共聚物(A1)、即接枝共聚物之主幹成分，進而較佳為使用具有羥基之多官能(甲基)丙烯酸酯作為交聯劑(B)。 Therefore, from the viewpoint of preventing moist heat and whitening, it is preferable to include a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as the main component of the acrylic copolymer (A1), that is, the graft copolymer. It is more preferable to use a polyfunctional (meth) acrylate having a hydroxyl group as the crosslinking agent (B).

交聯劑(B1)之含量並無特別限制。作為標準，較佳為相對於丙烯酸系共聚物(A1)100質量份為0.5~20質量份、其中為1質量份以上或15質量份以下、且其中為2質量份以上或10質量份以下之比率。 The content of the crosslinking agent (B1) is not particularly limited. As a standard, 0.5 to 20 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A1), preferably 1 part by mass or more or 15 parts by mass or less, and preferably 2 parts by mass or more and 10 parts by mass or less are preferred. ratio.

藉由以上述範圍含有交聯劑(B1)，可兼顧未交聯狀態下之本黏著片材之形狀穩定性與交聯後之黏著材之耐發泡可靠性。但，亦可出於與其他要素之平衡而超出該範圍。 By including the cross-linking agent (B1) in the above range, the shape stability of the present adhesive sheet in the uncrosslinked state and the foaming reliability of the cross-linked adhesive material can be taken into consideration. However, this range can also be exceeded for balance with other factors.

(光聚合起始劑(C1)) (Photopolymerization initiator (C1))

光聚合起始劑(C1)係發揮作為上述交聯劑(B1)之交聯反應中之反應起始助劑之功能者，可適當地使用關於上述光聚合起始劑(C)所記載者。 The photopolymerization initiator (C1) functions as a reaction initiation aid in the crosslinking reaction of the above-mentioned crosslinking agent (B1), and those described in the above-mentioned photopolymerization initiator (C) can be appropriately used. .

光聚合起始劑(C1)之含量並無特別限制。作為標準，較佳為以相對於丙烯酸系共聚物(A1)100質量份為0.1~10質量份、其中為0.5質量份以上或5質量份以下、且其中為1質量份以上或3質量份以下之比率含有。 The content of the photopolymerization initiator (C1) is not particularly limited. As a standard, it is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A1), of which 0.5 part by mass or more or 5 parts by mass or less, and 1 part by mass or more or 3 parts by mass or less is preferred. The ratio contains.

藉由將光聚合起始劑(C1)之含量設為上述範圍，可獲得適度之對於活性能量線之反應感度。 By setting the content of the photopolymerization initiator (C1) to the above range, a moderate response sensitivity to the active energy ray can be obtained.

(波長轉換劑(D1)) (Wavelength Converter (D1))

波長轉換劑(D1)係發揮促進印刷隱蔽部等光難以到達之部位之光硬化反應之功能者，可適當地使用關於上述波長轉換劑(D)所記載者。 The wavelength conversion agent (D1) functions to promote the photocuring reaction of the hard-to-reach areas such as the printing concealed portion, and those described in the above-mentioned wavelength conversion agent (D) can be used appropriately.

波長轉換劑(D1)之含量並無特別限制，較佳為以相對於丙烯酸系共聚物(A1)100質量份為0.001~2質量份、其中為0.002質量份以上或1.5質量份以下、且其中為0.004質量份以上或1質量份以下之比率含有。 The content of the wavelength conversion agent (D1) is not particularly limited, but it is preferably 0.001 to 2 parts by mass based on 100 parts by mass of the acrylic copolymer (A1), of which 0.002 parts by mass or more or 1.5 parts by mass or less, and among them It is contained in a ratio of 0.004 parts by mass or more or 1 part by mass or less.

(其他成分) (Other ingredients)

黏著劑組合物(I)亦可含有通常之黏著劑組合物中所調配之公知之成分作為上述以外之成分。例如可視需要適當地含有黏著賦予樹脂、或抗氧化劑、光穩定化劑、紫外線吸收劑、金屬減活劑、防銹劑、防老化劑、吸濕劑、發泡劑、消泡劑、無機粒子、黏度調整劑等各種添加劑。 The adhesive composition (I) may contain a well-known component blended in a general adhesive composition as a component other than the above. For example, it may contain an adhesion-imparting resin, or an antioxidant, a light stabilizer, an ultraviolet absorber, a metal deactivator, a rust inhibitor, an anti-aging agent, a hygroscopic agent, a foaming agent, a defoamer, and inorganic particles, as appropriate. , Viscosity modifiers and other additives.

又，亦可視需要適當地含有反應觸媒(三級胺系化合物、四級銨系 化合物、月桂酸錫化合物等)。 If necessary, a reaction catalyst (a tertiary amine compound, a quaternary ammonium compound, etc.) may be appropriately contained. Compounds, tin laurate compounds, etc.).

<黏著劑組合物(II)> <Adhesive composition (II)>

作為黏著劑組合物(II)，可列舉含有如下之基礎聚合物(A2)、交聯劑(B2)、光聚合起始劑(C2)、及波長轉換劑(D2)之樹脂組合物，該基礎聚合物(A2)含有玻璃轉移溫度(Tg)未達0℃之單體a、玻璃轉移溫度(Tg)為0℃以上且未達80℃之單體b、及玻璃轉移溫度(Tg)為80℃以上之單體c以a：b：c=10~40：90~35：0~25之莫耳比率進行共聚合而成且重量平均分子量為50000~400000之(甲基)丙烯酸酯共聚物或乙烯系共聚物。 Examples of the adhesive composition (II) include a resin composition containing the following base polymer (A2), a crosslinking agent (B2), a photopolymerization initiator (C2), and a wavelength conversion agent (D2). The base polymer (A2) contains a monomer a having a glass transition temperature (Tg) of less than 0 ° C, a monomer b having a glass transition temperature (Tg) of 0 ° C or more and less than 80 ° C, and a glass transition temperature (Tg) of A monomer (c) above 80 ° C is copolymerized at a molar ratio of a: b: c = 10 ~ 40: 90 ~ 35: 0 ~ 25, and a (meth) acrylate copolymer having a weight average molecular weight of 50,000 to 400,000 Or vinyl copolymer.

再者，所謂基礎聚合物係指構成黏著劑組合物(II)之主成分之樹脂。雖並非規定具體之含量者，但作為標準係占黏著劑組合物(II)中所含之樹脂之50質量%以上、其中為80質量%以上、且其中為90質量%以上(包括100質量%)的樹脂(再者，於基礎聚合物為2種以上之情形時，其等之合計量相當於上述含量)。 The base polymer refers to a resin constituting the main component of the adhesive composition (II). Although it is not a specific content, it is 50% by mass or more, 80% by mass or more, and 90% by mass or more (including 100% by mass) of the resin contained in the adhesive composition (II) as a standard. ) Resin (in addition, when there are two or more kinds of base polymers, the total amount thereof is equivalent to the above content).

(基礎聚合物(A2)) (Base polymer (A2))

基礎聚合物(A2)較佳為(甲基)丙烯酸酯共聚物或乙烯系共聚物。 The base polymer (A2) is preferably a (meth) acrylate copolymer or an ethylene-based copolymer.

就兼顧室溫狀態下之形狀保持性與熱熔性之觀點而言，上述(甲基)丙烯酸酯共聚物或乙烯系共聚物之重量平均分子量較佳為50000~400000，其中，進而較佳為60000以上或350000以下，且其中為70000以上或300000以下。 From the viewpoint of considering both shape retention and hot-melt properties at room temperature, the weight average molecular weight of the (meth) acrylate copolymer or ethylene-based copolymer is preferably 50,000 to 400,000, and more preferably More than 60,000 or less than 350,000, and among them 70,000 or less than 300,000.

丙烯酸酯系共聚物可藉由適當地選擇用以對其進行調整之丙烯酸系單體或甲基丙烯酸系單體之種類、組成比率、以及聚合條件等，而適當地調整玻璃轉移溫度(Tg)或分子量等物性。 The acrylic copolymer can appropriately adjust the glass transition temperature (Tg) by appropriately selecting the type, composition ratio, and polymerization conditions of the acrylic monomer or methacrylic monomer used to adjust it. Or molecular weight and other physical properties.

此時，作為構成丙烯酸酯共聚物之丙烯酸系單體，例如可列舉丙烯酸2-乙基己酯、丙烯酸正辛酯、丙烯酸異辛酯、丙烯酸正丁酯、丙烯酸乙酯等作為主原料。 In this case, as an acrylic monomer which comprises an acrylate copolymer, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-butyl acrylate, ethyl acrylate, etc. are mentioned as a main raw material.

除該等以外，亦可根據賦予凝聚力或賦予極性等目的而使具有各種官能基之(甲基)丙烯酸系單體與上述丙烯酸系單體共聚合。 In addition to these, a (meth) acrylic monomer having various functional groups and the above-mentioned acrylic monomer may be copolymerized for the purpose of imparting cohesion or giving polarity.

作為該具有官能基之(甲基)丙烯酸系單體，例如可列舉甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸羥基乙酯、丙烯酸、丙烯酸縮水甘油酯、N-取代丙烯醯胺、丙烯腈、甲基丙烯腈、含氟丙烯酸烷基酯、含有機矽氧烷基之丙烯酸酯等。 Examples of the (meth) acrylic monomer having a functional group include methyl methacrylate, methyl acrylate, hydroxyethyl acrylate, acrylic acid, glycidyl acrylate, N-substituted acrylamide, acrylonitrile, Methacrylonitrile, fluorine-containing alkyl acrylate, organosilyl-containing acrylate and the like.

另一方面，作為乙烯系共聚物，可列舉亦將可與上述丙烯酸系單體或甲基丙烯酸系單體進行共聚合之乙酸乙烯酯、或烷基乙烯基醚、羥基烷基乙烯基醚等各種乙烯基單體適當地聚合而成之乙烯系共聚物。 On the other hand, examples of the ethylene-based copolymer include vinyl acetate, alkyl vinyl ether, and hydroxyalkyl vinyl ether that can be copolymerized with the acrylic monomer or methacrylic monomer. An ethylene-based copolymer obtained by appropriately polymerizing various vinyl monomers.

作為本黏著片材之基礎聚合物(A2)，較佳為玻璃轉移溫度(Tg)未達0℃之單體a、玻璃轉移溫度(Tg)為0℃以上且未達80℃之單體b、及玻璃轉移溫度(Tg)為80℃以上之單體c以a：b：c=10~40：90~35：0~25之莫耳比率進行共聚合而成之(甲基)丙烯酸酯共聚物或乙烯系共聚物。 As the base polymer (A2) of the adhesive sheet, monomers a having a glass transition temperature (Tg) of less than 0 ° C, and monomers b having a glass transition temperature (Tg) of 0 ° C or more and less than 80 ° C are preferred. And (meth) acrylic acid ester copolymerized with a monomer c having a glass transition temperature (Tg) of 80 ° C or higher at a molar ratio of a: b: c = 10 ~ 40: 90 ~ 35: 0 ~ 25 Copolymer or ethylene-based copolymer.

此時，單體a、b及c之各玻璃轉移溫度(Tg)意指由該單體製作聚合物時(均聚物化)之各玻璃轉移溫度(Tg)。 At this time, each glass transition temperature (Tg) of the monomers a, b, and c means each glass transition temperature (Tg) when the polymer is produced (homopolymerized) from the monomer.

上述單體a較佳為具備具有例如碳數4以上之側鏈之烷基結構之(甲基)丙烯酸酯單體。 The monomer a is preferably a (meth) acrylate monomer having an alkyl structure having, for example, a side chain having 4 or more carbon atoms.

此時，碳數4以上之側鏈既可為包含直鏈者，亦可為包含分支之碳鏈者。 At this time, the side chain having a carbon number of 4 or more may be either a straight chain or a branched carbon chain.

更具體而言，上述單體a較佳為具有碳數4~10之直鏈烷基結構之(甲基)丙烯酸酯單體或者具有碳數6~18之分支烷基結構之(甲基)丙烯酸酯單體。 More specifically, the monomer a is preferably a (meth) acrylic acid ester monomer having a linear alkyl structure having 4 to 10 carbon atoms or a (meth) acrylic acid having a branched alkyl structure having 6 to 18 carbon atoms. Acrylic monomer.

此處，作為「具有碳數4~10之直鏈烷基結構之(甲基)丙烯酸酯單體」，可列舉(甲基)丙烯酸正丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯 酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸正癸酯等。 Here, as the "(meth) acrylate monomer having a linear alkyl structure having 4 to 10 carbon atoms", n-butyl (meth) acrylate, n-hexyl (meth) acrylate, and (meth) ) Acrylic N-octyl acid, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, and the like.

另一方面，作為「具有碳數6~18之分支烷基結構之(甲基)丙烯酸酯單體」，可列舉(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-甲基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸異硬脂酯等。 On the other hand, examples of the "(meth) acrylate monomer having a branched alkyl structure having 6 to 18 carbon atoms" include 2-ethylhexyl (meth) acrylate and 2-methyl (meth) acrylate Hexyl ester, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, and the like.

上述單體b較佳為碳數4以下之(甲基)丙烯酸酯單體、於側鏈具有環狀骨架之(甲基)丙烯酸酯單體、碳數4以下之乙烯基單體、或於側鏈具有環狀骨架之乙烯基單體。 The monomer b is preferably a (meth) acrylate monomer having a carbon number of 4 or less, a (meth) acrylate monomer having a cyclic skeleton in a side chain, a vinyl monomer having a carbon number of 4 or less, or A vinyl monomer having a cyclic skeleton in a side chain.

其中，上述單體b特佳為側鏈之碳數為4以下之乙烯基單體。 Among them, the monomer b is particularly preferably a vinyl monomer having a carbon number of 4 or less in the side chain.

此處，作為「碳數4以下之(甲基)丙烯酸酯單體」，可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異丁酯等。 Here, as the "(meth) acrylate monomer having 4 or less carbon atoms", methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) ) N-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, third butyl (meth) acrylate, isobutyl (meth) acrylate, and the like.

作為「於側鏈具有環狀骨架之(甲基)丙烯酸酯單體」，可列舉(甲基)丙烯酸異基酯、(甲基)丙烯酸環己酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、3,3,5-三甲基環己醇(甲基)丙烯酸酯、環狀三羥甲基丙烷縮甲醛(甲基)丙烯酸酯、4-乙氧基化異丙苯基苯酚(甲基)丙烯酸酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸二環戊烯酯等。 Examples of the "(meth) acrylic acid monomer having a cyclic skeleton in a side chain" include (meth) acrylic acid Ester, cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, benzyl (meth) acrylate, (meth) Phenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3,3,5-trimethylcyclohexanol (meth) acrylate, cyclic trimethylolpropane Formal (meth) acrylate, 4-ethoxylated cumene phenol (meth) acrylate, dicyclopentenyloxy (meth) acrylate, dicyclopentene (meth) acrylate Esters, etc.

作為「碳數4以下之乙烯基單體」，可列舉乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、正丙基乙烯醚、異丙基乙烯醚、正丁基乙烯醚、異丁基乙烯醚等。 Examples of the "vinyl monomer having a carbon number of 4 or less" include vinyl acetate, vinyl propionate, vinyl butyrate, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl Vinyl ether, etc.

作為「於側鏈具有環狀骨架之乙烯基單體」，可列舉苯乙烯、環己基乙烯醚、降基乙烯醚、降烯基乙烯醚等。其中，特佳為側鏈之碳數為4以下之乙烯基單體、或側鏈之碳數為4以下之丙烯酸酯單體。 Examples of the "vinyl monomer having a cyclic skeleton in the side chain" include styrene, cyclohexyl vinyl ether, and Vinyl vinyl ether Alkenyl vinyl ether and the like. Among them, a vinyl monomer having a carbon number of 4 or less in the side chain or an acrylate monomer having 4 or less carbon in the side chain is particularly preferred.

上述單體c較佳為側鏈之碳數為1以下之(甲基)丙烯酸酯單體、或於側鏈具有環狀骨架之(甲基)丙烯酸酯單體。 The monomer c is preferably a (meth) acrylate monomer having a carbon number of 1 or less in the side chain, or a (meth) acrylate monomer having a cyclic skeleton in the side chain.

此處，作為「側鏈之碳數為1以下之(甲基)丙烯酸酯單體」，可列舉甲基丙烯酸甲酯、丙烯酸、甲基丙烯酸等。 Here, as "(meth) acrylate monomer whose carbon number of a side chain is 1 or less", methyl methacrylate, acrylic acid, methacrylic acid, etc. are mentioned.

作為「於側鏈具有環狀骨架之(甲基)丙烯酸酯單體」，可列舉甲基丙烯酸異基酯、甲基丙烯酸3,3,5-三甲基環己酯、丙烯酸二環戊酯、甲基丙烯酸二環戊酯、甲基丙烯酸二環戊烯酯等。 Examples of the "(meth) acrylate monomer having a cyclic skeleton in the side chain" include methacrylic acid Base ester, 3,3,5-trimethylcyclohexyl methacrylate, dicyclopentyl acrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, and the like.

若基礎聚合物(A2)含有單體a、單體b、單體c以a：b：c=10~40：90~35：0~25之莫耳比率進行共聚合而成之(甲基)丙烯酸酯共聚物或乙烯系共聚物，則可將Tanδ之峰值調整為0~20℃，於通常狀態、即室溫狀態下，可保持片狀之形狀。並且，可表現出能剝離之程度之接著性(稱作“黏性”)。又，若加熱至可熱熔之溫度，則表現出流動性，可追隨貼合面之階差部而填充至各個角落。 If the base polymer (A2) contains monomer a, monomer b, and monomer c and copolymerized at a molar ratio of a: b: c = 10 ~ 40: 90 ~ 35: 0 ~ 25 (methyl ) Acrylic acid ester copolymer or ethylene-based copolymer, the peak value of Tan δ can be adjusted to 0 ~ 20 ° C, and the sheet shape can be maintained in a normal state, that is, a room temperature state. In addition, adhesiveness (called "stickiness") to the extent that it can be peeled off can be exhibited. In addition, if it is heated to a temperature at which it can be melted, it exhibits fluidity and can be filled in every corner following the stepped portion of the bonding surface.

因此，就該觀點而言，構成基礎聚合物(A2)之(甲基)丙烯酸酯共聚物或乙烯系共聚物中之單體a、單體b、及單體c之莫耳比率較佳為a：b：c=10~40：90~35：0~25，其中，較佳為13~40：87~35：0~23，且其中為15~40：85~38：2~20。 Therefore, from this viewpoint, the molar ratios of the monomers a, b, and c in the (meth) acrylate copolymer or the ethylene-based copolymer constituting the base polymer (A2) are preferably a: b: c = 10 ~ 40: 90 ~ 35: 0 ~ 25, among which 13 ~ 40: 87 ~ 35: 0 ~ 23 is preferred, and 15 ~ 40: 85 ~ 38: 2 ~ 20 are among them.

又，就與上述同樣之觀點而言，構成基礎聚合物(A2)之(甲基)丙烯酸酯共聚物或乙烯系共聚物中之單體a、單體b、及單體c之莫耳比率較佳為b>a>c。 From the same viewpoints as described above, the molar ratios of the monomers a, b, and c in the (meth) acrylate copolymer or ethylene-based copolymer constituting the base polymer (A2) are as follows. Preferably, b> a> c.

(交聯劑(B2)) (Crosslinking agent (B2))

藉由使交聯劑(B2)於本黏著片材中交聯，本黏著片材可表現出高溫環境下之較高之凝聚力，可獲得優異之耐發泡可靠性。 By cross-linking the cross-linking agent (B2) in the adhesive sheet, the adhesive sheet can exhibit high cohesion under high-temperature environments and can obtain excellent foaming reliability.

作為此種交聯劑(B2)，例如可適當地選擇環氧交聯劑或異氰酸酯交聯劑、包含氧雜環丁烷化合物、矽烷化合物、丙烯酸系化合物等之交聯劑。其中，就反應性或所獲得之硬化物之強度之方面而言，較佳 為具有2個以上、其中為3個以上之(甲基)丙烯醯基之多官能(甲基)丙烯酸酯。 As such a crosslinking agent (B2), an epoxy crosslinking agent or an isocyanate crosslinking agent, a crosslinking agent containing an oxetane compound, a silane compound, an acrylic compound, etc. can be selected suitably, for example. Among them, it is preferable in terms of reactivity or strength of the obtained hardened material. It is a polyfunctional (meth) acrylate having two or more (meth) acrylfluorenyl groups.

作為此種多官能(甲基)丙烯酸酯，例如可列舉1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、甘油縮水甘油醚二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、雙酚A聚乙氧基二(甲基)丙烯酸酯、雙酚A聚烷氧基二(甲基)丙烯酸酯、雙酚F聚烷氧基二(甲基)丙烯酸酯、聚伸烷基二醇二(甲基)丙烯酸酯、三羥甲基丙烷三氧基乙基(甲基)丙烯酸酯、ε-己內酯改性三(2-羥基乙基)異氰尿酸酯三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、烷氧基化季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、烷氧基化季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、烷氧基化二季戊四醇六(甲基)丙烯酸酯、聚伸烷基二醇二(甲基)丙烯酸酯、異氰尿酸三(丙烯醯氧基乙基)酯、二季戊四醇五(甲基)丙烯酸酯、烷氧基化二季戊四醇五(甲基)丙烯酸酯、三季戊四醇六(甲基)丙烯酸酯、三季戊四醇五(甲基)丙烯酸酯、羥基特戊酸新戊二醇二(甲基)丙烯酸酯、羥基特戊酸新戊二醇酯之ε-己內酯加成物之二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、烷氧基化三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯等紫外線硬化型之多官能單體類、以及聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯、聚醚(甲基)丙烯酸酯等多官能丙烯酸系低聚物類。 Examples of such a polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and glycerol di (meth) acrylate , Glycerol glycidyl ether di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol (Meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polyalkoxydi (meth) acrylate, bisphenol F polyalkoxydi (meth) acrylic acid Ester, polyalkylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ε-caprolactone modified tri (2-hydroxyethyl) isocyanate Uric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, alkoxylated pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, alkoxylated pentaerythritol tetra (methyl) Acrylate), dipentaerythritol hexa (meth) acrylate, alkoxylated dipentaerythritol hexa (meth) acrylate, polyalkylene glycol di (meth) acrylate, isocyanuric acid tris (acrylic acid) Oxy Base) ester, dipentaerythritol penta (meth) acrylate, alkoxylated dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, hydroxy Neopentyl glycol valerate di (meth) acrylate, ε-caprolactone adduct of neopentyl glycol valerate, di (meth) acrylate, trimethylolpropane tri (methyl) ) UV-curable polyfunctional monomers such as acrylate, alkoxylated trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, and polyester ( Multifunctional acrylic oligomers such as (meth) acrylate, epoxy (meth) acrylate, (meth) acrylate urethane, and polyether (meth) acrylate.

上述列舉中，就提高對被黏著體之密接性或耐熱性、抑制濕熱白化之效果之觀點而言，較佳為含有極性官能基之多官能單體或低聚物。其中，較佳為使用具有異三聚氰酸環骨架之多官能(甲基)丙烯酸酯。 Among the above examples, from the viewpoints of improving the adhesion to the adherend or the heat resistance and suppressing the effects of moist heat and whitening, a polyfunctional monomer or oligomer containing a polar functional group is preferred. Among these, it is preferable to use a polyfunctional (meth) acrylate having an isocyanuric ring skeleton.

交聯劑(B2)之含量並無特別限制。作為標準，較佳為相對於基礎 聚合物(A2)100質量份為0.5~20質量份、其中為1質量份以上或15質量份以下、且其中為2質量份以上或10質量份以下之比率。 The content of the crosslinking agent (B2) is not particularly limited. As a standard, preferably relative to the foundation The ratio of 100 parts by mass of the polymer (A2) is 0.5 to 20 parts by mass, of which 1 part by mass or more or 15 parts by mass or less, and 2 parts by mass or more or 10 parts by mass or less.

藉由以上述範圍含有交聯劑(B2)，可兼顧未交聯狀態下之本黏著片材之形狀穩定性與交聯後之黏著片材中之耐發泡可靠性。但，亦可出於與其他要素之平衡而超出該範圍。 By including the cross-linking agent (B2) in the above range, the shape stability of the present adhesive sheet in the uncrosslinked state and the foaming resistance in the crosslinked adhesive sheet can be taken into consideration. However, this range can also be exceeded for balance with other factors.

(光聚合起始劑(C2)) (Photopolymerization initiator (C2))

光聚合起始劑(C2)係發揮作為上述交聯劑(B2)之交聯反應中之反應起始助劑之功能者，可適當地使用關於上述光聚合起始劑(C)所記載者。 The photopolymerization initiator (C2) functions as a reaction initiation aid in the crosslinking reaction of the above-mentioned crosslinking agent (B2), and those described in the above-mentioned photopolymerization initiator (C) can be appropriately used. .

光聚合起始劑(C2)之含量並無特別限制。作為標準，較佳為以相對於基礎聚合物(A2)100質量份為0.1~10質量份、其中為0.5質量份以上或5質量份以下、且其中為1質量份以上或3質量份以下之比率含有。 The content of the photopolymerization initiator (C2) is not particularly limited. As a standard, it is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the base polymer (A2), of which 0.5 part by mass or more or 5 parts by mass or less, and among which 1 part by mass or more or 3 parts by mass or less are preferred. The ratio contains.

藉由將光聚合起始劑(C2)之含量設為上述範圍，可獲得適度之對於活性能量線之反應感度。 By setting the content of the photopolymerization initiator (C2) to the above range, a moderate response sensitivity to the active energy ray can be obtained.

(波長轉換劑(D2)) (Wavelength Converter (D2))

波長轉換劑(D2)係發揮促進印刷隱蔽部等光難以到達之部位之光硬化反應之功能者，可適當地使用關於上述波長轉換劑(D)所記載者。 The wavelength conversion agent (D2) functions to promote the photocuring reaction of hard-to-reach areas such as the print concealed portion, and those described in the above-mentioned wavelength conversion agent (D) can be appropriately used.

波長轉換劑(D2)之含量並無特別限制，較佳為以相對於基礎聚合物(A2)100質量份為0.001~2質量份、其中為0.002質量份以上或1.5質量份以下、且其中為0.004質量份以上或1質量份以下之比率含有。 The content of the wavelength conversion agent (D2) is not particularly limited, but it is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the base polymer (A2), of which 0.002 parts by mass or more or 1.5 parts by mass or less, where It is contained in a ratio of 0.004 parts by mass or more and 1 part by mass or less.

(其他成分) (Other ingredients)

黏著劑組合物(II)亦可含有通常之黏著劑組合物中所調配之公知之成分作為上述以外之成分。例如可視需要適當地含有黏著賦予樹脂、或抗氧化劑、光穩定化劑、紫外線吸收劑、金屬減活劑、防銹劑、防老化劑、吸濕劑、發泡劑、消泡劑、無機粒子、黏度調整劑等各種添加劑。 The adhesive composition (II) may contain a well-known component blended in a general adhesive composition as a component other than the above. For example, it may contain an adhesion-imparting resin, or an antioxidant, a light stabilizer, an ultraviolet absorber, a metal deactivator, a rust inhibitor, an anti-aging agent, a hygroscopic agent, a foaming agent, a defoamer, and inorganic particles, as appropriate , Viscosity modifiers and other additives.

又，亦可視需要適當地含有反應觸媒(三級胺系化合物、四級銨系化合物、月桂酸錫化合物等)。 Moreover, if necessary, a reaction catalyst (a tertiary amine compound, a quaternary ammonium compound, a tin laurate compound, etc.) may be appropriately contained.

<詞句之說明> <Explanation of words>

本說明書中，於表達為「X~Y」(X、Y係任意之數字)之情形時，只要未特別說明，則為「X以上且Y以下」之含義，並且亦包含「較佳為大於X」或「較佳為小於Y」之含義。 In this specification, when it is expressed as "X ~ Y" (X and Y are arbitrary numbers), unless otherwise specified, it means "above X and below Y" and also includes "preferably greater than "X" or "preferably less than Y".

又，於表達為「X以上」(X係任意之數字)或「Y以下」(Y係任意之數字)之情形時，亦包含「較佳為大於X」或者「較佳為未達Y」之意圖。 In addition, when the expression is "above X" (X is an arbitrary number) or "below Y" (Y is an arbitrary number), it also includes "preferably greater than X" or "preferably less than Y" The intention.

又，通常所謂「片材」，於JIS中之定義上係指較薄、通常其厚度較長度與寬度而言小且平坦之製品，通常所謂「膜」係指與長度及寬度相比厚度極小，且最大厚度被任意地限定之薄且平坦之製品，通常以卷之形式供給(日本工業標準JIS K6900)。例如關於厚度而言，有狹義上將100μm以上者稱為片材，將未達100μm者稱為膜之情形。但，片材與膜之邊界不定，本發明中無需於詞句上區別兩者，因此，本發明中，即便於稱為「膜」之情形時，亦包含「片材」，即便於稱為「片材」之情形時，亦包含「膜」。 In addition, the so-called "sheet" generally refers to a product that is thinner, generally thinner and flatter than its length and width in the definition of JIS, and the "film" generally refers to its extremely small thickness compared to its length and width. Thin and flat products whose maximum thickness is arbitrarily defined are usually supplied in the form of rolls (Japanese Industrial Standard JIS K6900). For example, in terms of thickness, those having a thickness of 100 μm or more are referred to as a sheet, and those having a thickness of less than 100 μm are referred to as a film. However, the boundary between a sheet and a film is indefinite, and it is not necessary to distinguish between the two in terms of words and phrases in the present invention. Therefore, in the present invention, even when it is called a "film", it also includes a "sheet", even if it is called a "film" In the case of "sheet", "film" is also included.

實施例 Examples

以下，藉由實施例及比較例更加詳細地進行說明。但，本發明不限定於該等。 Hereinafter, examples and comparative examples will be described in more detail. However, the present invention is not limited to these.

[實施例1] [Example 1]

作為丙烯酸系共聚物(A)，使用數量平均分子量2400之聚甲基丙烯酸甲酯巨單體15重量份、丙烯酸丁酯81重量份、及丙烯酸4重量份進行無規共聚而成之丙烯酸酯共聚物(A-1)(重量平均分子量23萬)，對於該丙烯酸酯共聚物(A-1)1kg，均勻地混合作為交聯劑(B)之甘油二甲基丙烯酸酯(B-1)90g、作為光聚合起始劑(C)之Esacure KTO46(Lanberti公司 製造)(C-1)15g、及作為波長轉換劑(D)之2,5-雙(5-第三丁基-2-苯并唑)噻吩(TinopaOB，BASF公司製造)(D-1)0.1g，製作黏著劑樹脂組合物1。 As the acrylic copolymer (A), 15 parts by weight of a polymethyl methacrylate macromonomer having a number average molecular weight of 2,400, 81 parts by weight of butyl acrylate, and 4 parts by weight of acrylic acid were randomly copolymerized. (A-1) (weight average molecular weight 230,000), 90 g of glycerol dimethacrylate (B-1) as a crosslinking agent (B) was uniformly mixed with 1 kg of the acrylate copolymer (A-1) 15 g of Esacure KTO46 (manufactured by Lanberti) (C-1) as a photopolymerization initiator (C), and 2,5-bis (5-third butyl-2-benzene) as a wavelength conversion agent (D) and 0.1 g of azole) thiophene (TinopaOB, manufactured by BASF) (D-1), to prepare an adhesive resin composition 1.

利用經剝離處理之聚對苯二甲酸乙二酯膜(稱作「剝離膜1」。三菱樹脂公司製造之「DIAFOIL MRV-V06」，厚度100μm)與經剝離處理之聚對苯二甲酸乙二酯膜(稱作「剝離膜2」。三菱樹脂公司製造之「DIAFOIL MRQ」，厚度75μm)之2片剝離膜1、2夾持上述黏著劑樹脂組合物1，使用貼合機以成為厚度200μm之方式成形為片狀，製作黏著片材1。 Using a peeled polyethylene terephthalate film (referred to as "Release Film 1". "DIAFOIL MRV-V06" manufactured by Mitsubishi Resin Co., Ltd., thickness 100 µm) and a peeled polyethylene terephthalate Ester film (referred to as "release film 2". "DIAFOIL MRQ" manufactured by Mitsubishi Resin Co., Ltd., thickness: 75 μm) Two release films 1 and 2 sandwiched the above-mentioned adhesive resin composition 1 and used a bonding machine to have a thickness of 200 μm In this way, it is formed into a sheet shape, and an adhesive sheet 1 is produced.

再者，作為波長轉換劑(D)之2,5-雙(5-第三丁基-2-苯并唑)噻吩(D-1)係有機系之螢光體，具有相溶於丙烯酸系共聚物(A-1)之性質。 In addition, as a wavelength conversion agent (D), 2,5-bis (5-third butyl-2-benzo) The azole) thiophene (D-1) organic phosphor is compatible with the acrylic copolymer (A-1).

上述丙烯酸系共聚物(A-1)係包含具備巨單體作為分支成分之接枝共聚物之(甲基)丙烯酸酯共聚物之一種。上述黏著劑樹脂組合物1具有於未交聯狀態下藉由加熱而軟化或流動之熱熔性，並且具有藉由光而進行交聯之光交聯性。 The acrylic copolymer (A-1) is one of (meth) acrylate copolymers including a graft copolymer having a macromonomer as a branching component. The above-mentioned adhesive resin composition 1 has hot-melt properties which are softened or flowed by heating in an uncrosslinked state, and have photocrosslinkability which is crosslinked by light.

[實施例2] [Example 2]

將作為波長轉換劑(D)之2,5-雙(5-第三丁基-2-苯并唑)噻吩(TinopaOB，BASF公司製造)(D-1)之混合量變更為0.5g，除此以外，以與實施例1相同之方式製作黏著劑樹脂組合物2。 2,5-bis (5-tert-butyl-2-benzo) as wavelength conversion agent (D) An adhesive resin composition 2 was prepared in the same manner as in Example 1 except that the mixing amount of azole) thiophene (TinopaOB, manufactured by BASF) (D-1) was changed to 0.5 g.

並且，與實施例1同樣地利用剝離膜1、2夾持該黏著劑樹脂組合物2，使用貼合機以成為厚度150μm之方式成形為片狀，製作黏著片材2。 Then, the adhesive resin composition 2 was sandwiched by the release films 1 and 2 in the same manner as in Example 1. The adhesive resin composition 2 was formed into a sheet shape using a bonding machine so as to have a thickness of 150 μm, and an adhesive sheet 2 was produced.

[實施例3] [Example 3]

將作為波長轉換劑(D)之2,5-雙(5-第三丁基-2-苯并唑)噻吩(TinopaOB，BASF公司製造)(D-1)之混合量變更為1g，除此以外，以與實施例1相同之方式製作黏著劑樹脂組合物3。 2,5-bis (5-tert-butyl-2-benzo) as wavelength conversion agent (D) An adhesive resin composition 3 was produced in the same manner as in Example 1 except that the mixing amount of azole) thiophene (TinopaOB, manufactured by BASF) (D-1) was changed to 1 g.

並且，與實施例1同樣地利用剝離膜1、2夾持該黏著劑樹脂組合物3，使用貼合機以成為厚度125μm之方式成形為片狀，製作黏著片材3。 Then, the adhesive resin composition 3 was sandwiched by the release films 1 and 2 in the same manner as in Example 1. The adhesive resin composition 3 was formed into a sheet shape using a bonding machine so as to have a thickness of 125 μm, and an adhesive sheet 3 was produced.

[實施例4] [Example 4]

對於實施例1中所使用之丙烯酸酯共聚物(A-1)1kg，均勻地混合作為交聯劑(B)之三羥甲基丙烷環氧丙烯酸酯(B-2)100g、作為光聚合起始劑(C)之Esacure KTO46(Lanberti公司製造)(C-1)30g、及作為波長轉換劑(D)之2,5-雙(5-第三丁基-2-苯并唑)噻吩(D-1)0.2g，製作黏著劑樹脂組合物4。 About 1 kg of the acrylate copolymer (A-1) used in Example 1, 100 g of trimethylolpropane epoxy acrylate (B-2) as a cross-linking agent (B) were uniformly mixed, and photopolymerized as 30 g of Esacure KTO46 (manufactured by Lanberti) (C-1) as the initiator (C) and 2,5-bis (5-third-butyl-2-benzo) as the wavelength conversion agent (D) An azole) thiophene (D-1) was 0.2 g to prepare an adhesive resin composition 4.

並且，與實施例1同樣地利用剝離膜1、2夾持該黏著劑樹脂組合物4，使用貼合機以成為厚度150μm之方式成形為片狀，製作黏著片材4。 Then, the adhesive resin composition 4 was sandwiched by the release films 1 and 2 in the same manner as in Example 1. The adhesive resin composition 4 was formed into a sheet shape using a laminator so as to have a thickness of 150 μm, and an adhesive sheet 4 was produced.

再者，上述黏著劑樹脂組合物4具有於未交聯狀態下藉由加熱而軟化或流動之熱熔性，並且具有藉由光而進行交聯之光交聯性。 Moreover, the said adhesive resin composition 4 has the hot-melt property which softens or flows by heating in the non-crosslinked state, and has the photo-crosslinking property which cross-links by light.

[實施例5] [Example 5]

代替於實施例4中混合(C-1)30g而混合作為光聚合起始劑(C)之Esacure TZT(Lanberti公司製造)(C-2)15g，並且混合作為光增感劑之Esacure A198(Lanberti公司製造)50g，除此以外，以與實施例4相同之方式製作黏著劑樹脂組合物5。 Instead of mixing 30 g of (C-1) in Example 4, 15 g of Esacure TZT (manufactured by Lanberti) (C-2) as a photopolymerization initiator (C) was mixed, and Esacure A198 (a photosensitizer) was mixed An adhesive resin composition 5 was prepared in the same manner as in Example 4 except that 50 g was manufactured by Lanberti Corporation.

並且，與實施例1同樣地利用剝離膜1、2夾持該黏著劑樹脂組合物5，使用貼合機以成為厚度150μm之方式成形為片狀，製作黏著片材5。 Then, the adhesive resin composition 5 was sandwiched by the release films 1 and 2 in the same manner as in Example 1. The adhesive resin composition 5 was formed into a sheet shape using a laminator so as to have a thickness of 150 μm, and an adhesive sheet 5 was produced.

[實施例6] [Example 6]

代替於實施例1中混合波長轉換劑(D-1)0.1g而混合Hakkol PY1800(昭和化學工業股份有限公司製造)(D-2)1g作為波長轉換劑(D)，除此以外，以與實施例1相同之方式製成黏著劑樹脂組合物6。 Instead of mixing 0.1 g of the wavelength conversion agent (D-1) in Example 1, 1 g of Hakkol PY1800 (manufactured by Showa Chemical Industry Co., Ltd.) (D-2) was mixed as the wavelength conversion agent (D). In the same manner as in Example 1, an adhesive resin composition 6 was prepared.

並且，與實施例1同樣地利用剝離膜1、2夾持該黏著劑樹脂組合物6，使用貼合機以成為厚度150μm之方式成形為片狀，製作黏著片材6。 Then, the adhesive resin composition 6 was sandwiched by the release films 1 and 2 in the same manner as in Example 1. The adhesive resin composition 6 was formed into a sheet shape using a bonding machine so as to have a thickness of 150 μm, and an adhesive sheet 6 was produced.

再者，作為波長轉換劑(D)之Hakkol PY1800係有機系之螢光體，具有相溶於丙烯酸系共聚物(A-1)之性質。 Furthermore, the Hakkol PY1800 organic phosphor as a wavelength conversion agent (D) has a property of being compatible with the acrylic copolymer (A-1).

上述黏著劑樹脂組合物6具有於未交聯狀態下藉由加熱而軟化或流動之熱熔性，並且具有藉由光而進行交聯之光交聯性。 The above-mentioned adhesive resin composition 6 has a hot-melt property that softens or flows by heating in an uncrosslinked state, and has a photocrosslinkability that is crosslinked by light.

[實施例7] [Example 7]

代替於實施例1中混合波長轉換劑(D-1)0.1g而混合Hakkol PSR(昭和化學工業股份有限公司製造)(D-3)1g作為波長轉換劑(D)，除此以外，以與實施例1相同之方式製作黏著劑樹脂組合物7。 Instead of mixing 0.1 g of the wavelength conversion agent (D-1) in Example 1, 1 g of Hakkol PSR (manufactured by Showa Chemical Industry Co., Ltd.) (D-3) was mixed as the wavelength conversion agent (D). In the same manner as in Example 1, an adhesive resin composition 7 was produced.

並且，與實施例1同樣地利用剝離膜1、2夾持該黏著劑樹脂組合物7，使用貼合機以成為厚度150μm之方式成形為片狀，製作黏著片材7。 Then, the adhesive resin composition 7 was sandwiched by the release films 1 and 2 in the same manner as in Example 1, and formed into a sheet shape using a bonding machine so as to have a thickness of 150 μm, and an adhesive sheet 7 was produced.

再者，作為波長轉換劑(D)之Hakkol PSR係有機系之螢光體，具有相溶於丙烯酸系共聚物(A-1)之性質。 In addition, the Hakkol PSR organic phosphor as a wavelength conversion agent (D) has a property of being compatible with the acrylic copolymer (A-1).

上述黏著劑樹脂組合物7具有於未交聯狀態下藉由加熱而軟化或流動之熱熔性，並且具有藉由光而進行交聯之光交聯性。 The above-mentioned adhesive resin composition 7 has hot-melt properties which are softened or flowed by heating in an uncrosslinked state, and have photocrosslinkability which is crosslinked by light.

[實施例8] [Example 8]

作為乙烯系共聚物(A)，使用丙烯酸2-乙基己酯55重量份、乙酸乙烯酯40重量份、及丙烯酸5重量份進行無規共聚而成之乙烯系共聚物(A-2)(重量平均分子量：17萬)，對於該乙烯系共聚物(A-2)1kg，均勻地混合作為交聯劑(B)之(2,4,6-三側氧基-1,3,5-三氮雜環己烷-1,3,5-三基)三伸乙基三丙烯酸酯(B-3)(東亞合成製造，Aronix M315)75g、作為光聚合起始劑(C)之Esacure KTO46(C-1)(Lanberti公司製造)15g、及作為波長轉換劑(D)之2,5-雙(5-第三丁基-2-苯并唑)噻吩(TinopaOB， BASF公司製造)(D-1)0.2g，製作黏著劑樹脂組合物8。 As the ethylene-based copolymer (A), an ethylene-based copolymer (A-2) obtained by random copolymerization using 55 parts by weight of 2-ethylhexyl acrylate, 40 parts by weight of vinyl acetate, and 5 parts by weight of acrylic acid ( Weight average molecular weight: 170,000), 1 kg of the ethylene-based copolymer (A-2) was uniformly mixed as (2,4,6-trilateraloxy-1,3,5-) of the cross-linking agent (B) 75 g of triazacyclohexane-1,3,5-triyl) triethylene triacrylate (B-3) (manufactured by Toa Kosei, Aronix M315), Esacure KTO46 as a photopolymerization initiator (C) (C-1) 15 g (manufactured by Lanberti) and 2,5-bis (5-third butyl-2-benzo) as a wavelength conversion agent (D) An azole) thiophene (TinopaOB, manufactured by BASF) (D-1) 0.2 g, and an adhesive resin composition 8 was produced.

並且，與實施例1同樣地利用剝離膜1、2夾持該黏著劑樹脂組合物8，使用貼合機以成為厚度150μm之方式成形為片狀，製作黏著片材8。 Then, the adhesive resin composition 8 was sandwiched by the release films 1 and 2 in the same manner as in Example 1. The adhesive resin composition 8 was formed into a sheet shape using a bonding machine so as to have a thickness of 150 μm, and an adhesive sheet 8 was produced.

再者，作為波長轉換劑(D)之2,5-雙(5-第三丁基-2-苯并唑)噻吩(D-1)係有機系之螢光體，具有相溶於乙烯系共聚物(A-2)之性質。 In addition, as a wavelength conversion agent (D), 2,5-bis (5-third butyl-2-benzo) The azole) thiophene (D-1) organic phosphor is compatible with the vinyl copolymer (A-2).

上述乙烯系共聚物(A-2)係玻璃轉移溫度(Tg)未達0℃之單體a、玻璃轉移溫度(Tg)為0℃以上且未達80℃之單體b、及玻璃轉移溫度(Tg)為80℃以上之單體c以a：b：c=10~40：90~35：0~25之莫耳比率進行共聚合而成之乙烯系共聚物之一種。 The ethylene-based copolymer (A-2) is a monomer a having a glass transition temperature (Tg) of less than 0 ° C, a monomer b having a glass transition temperature (Tg) of 0 ° C or more and less than 80 ° C, and a glass transition temperature (Tg) is one of ethylene-based copolymers obtained by copolymerizing monomer c at 80 ° C or higher at a molar ratio of a: b: c = 10 ~ 40: 90 ~ 35: 0 ~ 25.

上述黏著劑樹脂組合物8具有於未交聯狀態下藉由加熱而軟化或流動之熱熔性，並且具有藉由光而進行交聯之光交聯性。 The above-mentioned adhesive resin composition 8 has a hot-melt property that softens or flows by heating in an uncrosslinked state, and has a photocrosslinkability that is crosslinked by light.

[實施例9] [Example 9]

使用對塗佈有紫外線吸收劑之聚對苯二甲酸乙二酯膜(三菱樹脂製造之「DIAFOIL O700E-100」、厚度100μm)實施剝離處理而成之膜(稱作「剝離膜3」)代替剝離膜1，除此以外，以與實施例2相同之方式製成黏著片材9。 A film (referred to as "release film 3") obtained by peeling a polyethylene terephthalate film ("DIAFOIL O700E-100" manufactured by Mitsubishi Resin, with a thickness of 100 µm) coated with an ultraviolet absorber (referred to as "release film 3") is used. Except for the release film 1, an adhesive sheet 9 was produced in the same manner as in Example 2.

[比較例1] [Comparative Example 1]

不添加2,5-雙(5-第三丁基-2-苯并唑)噻吩(TinopaOB，BASF公司製造)(D-1)作為波長轉換劑(D)，除此以外，以與實施例1相同之方式製成黏著劑組合物10。 No 2,5-bis (5-tert-butyl-2-benzo) added A pressure-sensitive adhesive composition 10 was prepared in the same manner as in Example 1 except that azole) thiophene (TinopaOB, manufactured by BASF) (D-1) was used as the wavelength conversion agent (D).

並且，與實施例1同樣地利用剝離膜1、2夾持該黏著劑樹脂組合物9，使用貼合機以成為厚度150μm之方式成形為片狀，製作黏著片材10。 Then, the adhesive resin composition 9 was sandwiched by the release films 1 and 2 in the same manner as in Example 1. The adhesive resin composition 9 was formed into a sheet shape using a bonding machine so as to have a thickness of 150 μm, and an adhesive sheet 10 was produced.

[比較例2] [Comparative Example 2]

對於實施例1中所使用之丙烯酸酯共聚物(A-1)1kg，均勻地混合 作為交聯劑(B)之三羥甲基丙烷環氧丙烯酸酯(B-2)90g、作為光聚合起始劑(C)之Esacure KTO46(Lanberti公司製造)(C-1)15g、及作為波長轉換劑(D)之2,5-雙(5-第三丁基-2-苯并唑)噻吩(D-1)2g，製作黏著劑樹脂組合物11。 About 1 kg of the acrylate copolymer (A-1) used in Example 1, 90 g of trimethylolpropane epoxy acrylate (B-2) as a cross-linking agent (B) was uniformly mixed. 15 g of Esacure KTO46 (manufactured by Lanberti) (C-1) as the initiator (C), and 2,5-bis (5-third butyl-2-benzo) as the wavelength conversion agent (D) 2 g of azole) thiophene (D-1) to prepare an adhesive resin composition 11.

並且，與實施例1同樣地利用剝離膜1、2夾持該黏著劑樹脂組合物11，使用貼合機以成為厚度150μm之方式成形為片狀，製作黏著片材11。 Then, the adhesive resin composition 11 was sandwiched by the release films 1 and 2 in the same manner as in Example 1. The adhesive resin composition 11 was formed into a sheet shape using a bonding machine so as to have a thickness of 150 μm, and an adhesive sheet 11 was produced.

[比較例3] [Comparative Example 3]

依據日本專利4971529號公報之實施例3製作黏著劑組合物12。 The adhesive composition 12 was prepared according to Example 3 of Japanese Patent No. 4971529.

即，於使丙烯酸2-乙基己酯75質量份、乙酸乙烯酯20質量份、及丙烯酸5質量份無規共聚而成之丙烯酸酯共聚物上述丙烯酸酯共聚物(A-3)1kg中混合添加作為交聯劑(B)之壬二醇二丙烯酸酯(V#260，大阪有機化學公司製造)(B-4)50g及作為光聚合起始劑(C)之4-甲基二苯甲酮(C-3)10g而製備黏著劑樹脂組合物12。 That is, 1 kg of the above-mentioned acrylate copolymer (A-3) was mixed with an acrylate copolymer obtained by randomly copolymerizing 75 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of vinyl acetate, and 5 parts by mass of acrylic acid. Added 50 g of nonanediol diacrylate (V # 260, manufactured by Osaka Organic Chemicals) (B-4) as a cross-linking agent (B) and 4-methyldibenzoyl as a photopolymerization initiator (C) 10 g of ketones (C-3) were used to prepare an adhesive resin composition 12.

並且，與實施例1同樣地利用剝離膜1、2夾持該黏著劑樹脂組合物12，使用貼合機以成為厚度150μm之方式成形為片狀。 In addition, the adhesive resin composition 12 was sandwiched between the release films 1 and 2 in the same manner as in Example 1, and was formed into a sheet shape using a bonding machine so as to have a thickness of 150 μm.

繼而，隔著聚對苯二甲酸乙二酯膜以波長365nm之紫外線達到1000mJ/cm2之方式對黏著層照射紫外線，使交聯劑局部反應，製作黏著片材12(厚度150μm)。 Then, the adhesive layer was irradiated with ultraviolet rays through a polyethylene terephthalate film so that ultraviolet rays having a wavelength of 365 nm reached 1000 mJ / cm 2 to locally react the crosslinking agent to produce an adhesive sheet 12 (150 μm in thickness).

[比較例4] [Comparative Example 4]

作為液狀接著劑樹脂組合物之比較例，對於聚異丁烯二丙烯酸酯低聚物(CN310，Arkema公司製造)460g，調整甲基丙烯酸異基酯(IB-X，共榮社化學公司製造)410g、及丙烯酸四氫呋喃甲酯(SR285，Arkema公司製造)130g之混合物，進而添加作為塑化劑之液狀聚丁二烯(RYCON134，Cray Valley公司製造)540g，進而，添加作為光聚合起始劑(C)之二苯基-2,4,6-三甲基苯甲醯基氧化膦(C-2)(Omnirad TPO，IGM公司製造)17g、1-羥基-環己基苯基酮(C-3)33g(Irgacure184，BASF公司製造)、及作為波長轉換劑(D)之2,5-雙(5-第三丁基-2-苯并唑)噻吩(D-1)0.16g而製作樹脂組合物13。再者，該組合物係液狀，無法成形為片材形狀。 As a comparative example of the liquid adhesive resin composition, 460 g of polyisobutylene diacrylate oligomer (CN310, manufactured by Arkema) was adjusted. A mixture of 410 g of base ester (IB-X, manufactured by Kyoeisha Chemical Co., Ltd.) and 130 g of tetrahydrofuran methyl acrylate (SR285, manufactured by Arkema), and a liquid polybutadiene (RYCON134, Cray Valley) was added as a plasticizer. 540 g), and diphenyl-2,4,6-trimethylbenzylidenephosphine oxide (C-2) (Omnirad TPO, manufactured by IGM) was added as a photopolymerization initiator (C). 17 g, 33 g of 1-hydroxy-cyclohexylphenyl ketone (C-3) (Irgacure184, manufactured by BASF), and 2,5-bis (5-third butyl-2-benzene) as a wavelength conversion agent (D) and 0.16 g of azole) thiophene (D-1) to prepare a resin composition 13. Furthermore, this composition is liquid and cannot be formed into a sheet shape.

[評價] [Evaluation]

對於實施例、比較例中所獲得之樣品，藉由以下方法對各項目進行評價。 The samples obtained in the examples and comparative examples were evaluated for each item by the following methods.

(凝膠分率) (Gel fraction)

於黑色片材(LSL-8 Inoac公司製造光線透過率0%)之單面貼附雙面膠帶，並切斷成50mm×200mm而製成遮光片材。 A black sheet (LSL-8 Inoac Co., Ltd. light transmittance 0%) was affixed to a double-sided tape on one side, and cut into 50 mm x 200 mm to produce a light-shielding sheet.

對於實施例1~8及比較例1~3中製成之黏著片材，於一剝離膜2之表面貼合上述遮光片材，製成將一部分隱蔽之積層體。但，對於比較例4之黏著劑組合物13，於將上述遮光片材貼合於剝離膜2而製作之帶有隱蔽部位之剝離膜2與剝離膜1之間，以成為厚度150μm之方式夾持黏著劑組合物13而製成積層體。 For the adhesive sheets prepared in Examples 1 to 8 and Comparative Examples 1 to 3, the above-mentioned light-shielding sheet was adhered to the surface of a release film 2 to form a laminated body in which a part was concealed. However, the adhesive composition 13 of Comparative Example 4 was sandwiched between the release film 2 with a concealed portion and the release film 1 produced by bonding the light-shielding sheet to the release film 2 so as to have a thickness of 150 μm. A laminated body was produced by holding the adhesive composition 13.

繼而，使用高壓水銀燈自以此方式製成之積層體之遮光片材側以波長365nm之累計光量成為2000mJ/cm2之方式對黏著劑組合物照射紫外線，使黏著劑組合物硬化。 Then, the light-shielding sheet side of the multilayer body produced in this way using a high-pressure mercury lamp was irradiated with ultraviolet rays to the adhesive composition so that the cumulative light amount at a wavelength of 365 nm became 2000 mJ / cm 2 to harden the adhesive composition.

對於光被遮蔽之部位，利用切割器將自遮光片材之長邊側端面至1mm之部位切斷，且僅將黏著劑組合物取出，對於如此所得者，使用下述方法測定凝膠分率。對於硬化前之黏著劑組合物及曝光部位之黏著劑組合物，亦以同樣之順序求出凝膠分率。 The light-shielded part was cut by a cutter from the long-side end surface of the light-shielding sheet to a position of 1 mm, and only the adhesive composition was taken out. For the obtained part, the gel fraction was measured using the following method . For the adhesive composition before curing and the adhesive composition at the exposed area, the gel fraction was also determined in the same order.

<凝膠分率測定方法> <Method for measuring gel fraction>

1)稱量黏著劑組合物(W1)，包於已預先測定重量之SUS絲網(W0)中。 1) Weigh the adhesive composition (W 1 ) and wrap it in a SUS screen (W 0 ) whose weight has been determined in advance.

2)將上述SUS絲網於100mL之乙酸乙酯中浸漬24小時。 2) The SUS screen was immersed in 100 mL of ethyl acetate for 24 hours.

3)將SUS絲網取出，於75℃下半乾燥4小時。 3) Take out the SUS screen and dry it at 75 ° C for 4 hours.

4)求出乾燥後之重量(W2)，根據下述式而測定黏著劑組合物之凝膠分率。 4) Determine the weight (W 2 ) after drying, and measure the gel fraction of the adhesive composition according to the following formula.

凝膠分率(%)=100×(W2-W0)/W1 Gel fraction (%) = 100 × (W 2 -W 0 ) / W 1

(接著力) (Advance force)

對於實施例1~8及比較例1~3中製成之黏著片材，將一剝離膜2剝下，並貼合50μm之PET(polyethylene terephthalate，聚對苯二甲酸乙二酯)膜(三菱樹脂公司製造之DIAFOIL T100、厚度50μm)作為襯底膜。 For the adhesive sheets prepared in Examples 1 to 8 and Comparative Examples 1 to 3, a peeling film 2 was peeled off, and a 50 μm PET (polyethylene terephthalate) film (Mitsubishi DIAFOIL T100 (50 μm thick) manufactured by Resin Company was used as the substrate film.

將上述積層品切斷成長度150mm、寬度10mm後，剝下殘留之剝離膜1，將露出之黏著面輥壓接於鈉鈣玻璃。 After cutting the laminated product to a length of 150 mm and a width of 10 mm, the remaining release film 1 was peeled off, and the exposed adhesive surface was roll-bonded to the soda-lime glass.

對以此方式而獲得之貼合品施加高壓釜處理(80℃，表壓0.2MPa，30分鐘)而最終貼附後，自襯底PET膜側以365nm之累計光量成為2000mJ/cm2之方式照射紫外線而使黏著片材硬化，於23℃、50%RH下熟化15小時而製成剝離力測定試樣。 An autoclave process (80 ° C, gauge pressure 0.2 MPa, 30 minutes) was applied to the bonded product obtained in this way, and after the final attachment, the cumulative light amount of 365 nm from the substrate PET film side became 2000 mJ / cm 2 The adhesive sheet was hardened by irradiating ultraviolet rays, and aged at 23 ° C. and 50% RH for 15 hours to prepare a peel force measurement sample.

對於比較例4之黏著劑組合物13，以成為厚度150μm之方式塗佈於鈉鈣玻璃上後，貼合作為襯底膜之50μmPET膜(三菱樹脂公司製造之DIAFOIL T100厚度50μm)。自襯底PET膜側以365nm之累計光量成為2000mJ/cm2之方式照射紫外線而使黏著片材硬化後，利用切割器以成為寬10mm之短條狀之方式於硬化物切出切口，製成剝離力測定試樣。 The adhesive composition 13 of Comparative Example 4 was applied to a soda-lime glass so as to have a thickness of 150 μm, and then a 50 μm PET film (diafoil T100 manufactured by Mitsubishi Resin Co., Ltd. with a thickness of 50 μm) was laminated. After curing the adhesive sheet by irradiating ultraviolet rays from the side of the substrate PET film so that the cumulative light amount of 365 nm becomes 2000 mJ / cm 2 , a cut is made into a hardened object with a width of 10 mm by a cutter to make a cut. Peel force measurement sample.

測定於23℃ 40%RH之環境下以剝離角180°、剝離速度60mm/分鐘剝離上述剝離力測定試樣時之對玻璃之剝離力(N/cm)。 The peeling force (N / cm) to glass when peeling the above-mentioned peeling force measurement sample at a peeling angle of 180 ° and a peeling speed of 60 mm / minute under an environment of 23 ° C and 40% RH was measured.

(階差追隨性) (Step following)

對60mm×90mm×厚度0.5mm之鈉鈣玻璃之周緣部實施寬度5mm、厚度40μm之印刷(總光線透過率0%)，製作於周緣部具有40μm之印刷階差之評價用玻璃基板。該評價用玻璃基板係於貼合面具有伴 有階差部之隱蔽部之圖像顯示裝置構成構件之代替品。 A 60 mm × 90 mm × 0.5 mm thick soda-lime glass was printed at a peripheral portion of a thickness of 5 mm and a thickness of 40 μm (total light transmittance 0%), and a glass substrate for evaluation having a printing step of 40 μm at the peripheral portion was produced. The glass substrate for evaluation is attached to the bonding surface. Substitute for constituent parts of image display device with hidden part with stepped part.

於上述玻璃基板之印刷面，將實施例1~8及比較例1~3中製成之黏著片材之一剝離膜2剝下而以使1kg之輥往返2次，且覆蓋周緣部之印刷階差之方式貼合黏著片材。繼而，將殘留之剝離膜1剝下，於減壓下(絕對壓力5kPa)且80℃下以加壓壓力0.02MPa將環烯烴聚合物膜(厚度100μm)加壓貼合於露出之黏著面後，實施高壓釜處理(60℃，0.2MPa，20分鐘)而最終貼附。 On the printed surface of the above glass substrate, peel off one of the release films 2 of the adhesive sheets prepared in Examples 1 to 8 and Comparative Examples 1 to 3 so that a 1 kg roller is reciprocated twice, and cover the peripheral edge of the print. Steps fit the adhesive sheet. Then, the remaining release film 1 was peeled off, and the cycloolefin polymer film (thickness: 100 μm) was pressure-bonded to the exposed adhesive surface under reduced pressure (absolute pressure: 5 kPa) and at a pressure of 0.02 MPa at 80 ° C. Then, an autoclave treatment (60 ° C, 0.2 MPa, 20 minutes) was performed and finally attached.

對於比較例4之樹脂組合物13，將樹脂組合物12以成為厚度150μm之方式直接塗佈於玻璃基板後，被覆環烯烴聚合物膜(厚度100μm)。對於上述積層體，使用高壓水銀燈自玻璃基板側以365nm之波長之光達到2000mJ/cm2之方式對黏著劑組合物照射紫外線。 In the resin composition 13 of Comparative Example 4, the resin composition 12 was directly applied to a glass substrate so as to have a thickness of 150 μm, and then a cycloolefin polymer film (thickness of 100 μm) was coated. The laminated body was irradiated with ultraviolet rays to the adhesive composition using a high-pressure mercury lamp so that light having a wavelength of 365 nm reached 2000 mJ / cm 2 from the glass substrate side.

以目視觀察所製成之積層體，將膜於階差附近彎曲而可觀察到因變形所致之凹凸不均者判定為「×」，將無氣泡而平滑地貼合者判定為「○」。 The laminated body produced by visual observation was judged as "×" if the film was bent near the step and the unevenness due to deformation was observed, and "○" was judged as a smooth adhesion without bubbles. .

(保管穩定性) (Storage stability)

對於階差追隨性評價中製成之評價用積層體，以目視觀察印刷部位之黏著劑組合物。 With respect to the laminated body for evaluation prepared in the step-following evaluation, the adhesive composition at the printed portion was visually observed.

利用85℃之烘箱加熱6小時後，亦以目視進行觀察，將印刷部位正下方之黏著劑組合物自加熱試驗前流動而溢出者判定為「×」，將加熱熟化後黏著劑組合物流動者判定為「△」，將通過加熱試驗未觀察到黏著之變形或溢出者判定為「○」。 After heating in an oven at 85 ° C for 6 hours, it was also visually observed. The adhesive composition directly under the printing area flowed before the heating test and overflowed as "×", and the adhesive composition after heating and curing flowed. It was judged as "△", and those with no adhesion deformation or overflow observed by the heating test were judged as "○".

(總光線透過率、霧度) (Total light transmittance, haze)

對於階差追隨性評價中製成之積層體，使用霧度計(日本電色工業股份有限公司製造NDH5000)，依據JIS K7361-1及JIS K7136測定總光線透過率以及霧度值。 For the laminated body produced in the step-following evaluation, the total light transmittance and the haze value were measured using a haze meter (NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7361-1 and JIS K7136.

(分光透過率、吸光度) (Spectral transmittance, absorbance)

對於階差追隨性評價中製成之積層體，使用分光光度計(島津製作所公司製造UV2000)，測定波長300nm~500nm之分光透過率(T%)。自390nm之波長之透過率根據下述式算出黏著片材之吸光度X，除以黏著片材厚度Y(mm)而求出X/Y。 For the multilayer body produced in the step-following evaluation, a spectrophotometer (UV2000 manufactured by Shimadzu Corporation) was used to measure the spectral transmittance (T%) at a wavelength of 300 nm to 500 nm. From the transmittance at a wavelength of 390 nm, the absorbance X of the adhesive sheet was calculated according to the following formula, and divided by the thickness Y (mm) of the adhesive sheet to obtain X / Y.

X=-Log(T/100) X = -Log (T / 100)

(剝離膜之分光透過率) (Spectral transmittance of release film)

對於實施例2、9中製作時所使用之剝離膜1、3，使用分光光度計(島津製作所公司製造、UV2000)測定波長300nm~500nm之分光透過率(T%)。 For the release films 1 and 3 used in the production of Examples 2 and 9, a spectrophotometer (manufactured by Shimadzu Corporation, UV2000) was used to measure the spectral transmittance (T%) at a wavelength of 300 nm to 500 nm.

又，對於實施例2、9中製作之黏著片材2、9，分別將上述黏著片材2以剝離膜1為上進行平置，將上述黏著片材9以剝離膜3為上進行平置，於螢光燈下(環境照度1170勒克司)保管1天。並且，依據上述凝膠分率測定方法算出保管1天後之黏著片材2、9之凝膠分率。將測定結果示於表2。 In addition, with respect to the adhesive sheets 2 and 9 prepared in Examples 2 and 9, the adhesive sheet 2 was placed on top of the release film 1 and the adhesive sheet 9 was placed on the release film 3 as the top. , Stored under fluorescent light (environmental illumination 1170 lux) for 1 day. Then, the gel fractions of the adhesive sheets 2 and 9 after storage for one day were calculated according to the gel fraction measurement method described above. The measurement results are shown in Table 2.

[考察] [Inspection]

可知，實施例之黏著劑組合物於貼合時具有較高之流動性，結果，不僅階差追隨性優異，亦由於波長轉換劑有助於促進隱蔽部位之硬化，故而印刷下部亦會進行硬化，且保管穩定性亦優異。 It can be seen that the adhesive composition of the example has high fluidity during bonding. As a result, not only is the step followability excellent, but also the wavelength conversion agent helps to promote the hardening of the hidden part, so the lower part of the printing will be hardened And excellent storage stability.

相對於此，比較例1由於不含波長轉換劑，故而結果為印刷階差部位之黏著劑組合物局部流動，難謂高溫下之保管穩定性充分。 In contrast, since Comparative Example 1 does not contain a wavelength conversion agent, the result is that the adhesive composition at the printing step portion flows locally, and it is difficult to say that the storage stability at high temperatures is sufficient.

比較例2中，由於波長轉換劑之吸光度較高，故而結果為光交聯所需之光未到達聚合組合物之深部，甚至於直接曝光之部位中光硬化反應亦未充分地進行。 In Comparative Example 2, since the absorbance of the wavelength conversion agent was high, as a result, the light required for photocrosslinking did not reach the deep part of the polymer composition, and the photohardening reaction did not proceed sufficiently even in the directly exposed part.

比較例3雖然不含波長轉換劑，但於貼合於構件之前已實施1次交聯，因此，獲得優異之保管穩定性，但於貼合時膜於階差附近彎曲而 未獲得充分之階差吸收性。 Although Comparative Example 3 did not contain a wavelength conversion agent, it was crosslinked once before bonding to the member. Therefore, excellent storage stability was obtained. However, the film was bent near the step during bonding. Insufficient step absorbency was obtained.

比較例4係液狀之黏著劑組合物，雖然由於可任意地流動而階差吸收性優異，但於印刷條件下等可觀察到難以硬化之部位之樹脂之溢出，保管穩定性不充分。又，由於不含丙烯酸系共聚物，故而硬化物無黏性，對被黏著體之接著力較差。再者，關於比較例4中之隱蔽部位之凝膠分率值，由於一部分以液狀殘留，故而無法自被黏著體將樹脂組合物全部採取，無法獲得準確之凝膠分率值。 In Comparative Example 4, the liquid adhesive composition was excellent in step absorbency because it could be arbitrarily flowed, but overflow of the resin in areas where it was difficult to harden was observed under printing conditions and the storage stability was insufficient. Moreover, since it does not contain an acrylic copolymer, hardened | cured material has no adhesiveness, and adhesive force to an adherend is inferior. In addition, regarding the gel fraction value of the concealed part in Comparative Example 4, since a part thereof remained in a liquid state, it was impossible to take all the resin composition from the adherend, and an accurate gel fraction value could not be obtained.

又，由實施例9之結果可知，藉由設為具備較波長380nm為短波長側之光之光線透過率為40%以下之剝離膜之構成，可抑制使用前之黏著片材進行凝膠化。 In addition, from the results of Example 9, it can be seen that the use of a peeling film having a light transmittance of 40% or less on the short-wavelength side of the wavelength of 380 nm can prevent gelation of the adhesive sheet before use. .

Claims (7)

一種透明黏著片材，其特徵係包含黏著劑組合物者，上述黏著劑組合物含有熱塑性樹脂(A)、交聯劑(B)、藉由至少波長380nm~430nm之光而反應之光聚合起始劑(C)、及被較波長380nm為短波長側之光激發而發出波長380nm~550nm之光之波長轉換劑(D)，其中：熱塑性樹脂(A)係包含具備巨單體作為分支成分之接枝共聚物之丙烯酸系共聚物，且波長390nm下之黏著片材之吸光度X與黏著片材之厚度Y滿足下述關係式(1)，式(1)...0.5≦X/Y≦12。A transparent adhesive sheet characterized by comprising an adhesive composition, said adhesive composition containing a thermoplastic resin (A), a cross-linking agent (B), and photopolymerized by photoreaction with light having a wavelength of at least 380 nm to 430 nm Initiator (C) and a wavelength conversion agent (D) that emits light with a wavelength of 380 nm to 550 nm when excited by light at a shorter wavelength side than 380 nm. The thermoplastic resin (A) contains a macromonomer as a branching component. The acrylic copolymer of the graft copolymer, and the absorbance X of the adhesive sheet at a wavelength of 390 nm and the thickness Y of the adhesive sheet satisfy the following relational formula (1), formula (1) ... 0.5 ≦ X / Y ≦ 12. 一種透明黏著片材，其特徵係包含黏著劑組合物者，上述黏著劑組合物含有熱塑性樹脂(A)、交聯劑(B)、藉由至少波長380nm~430nm之光而反應之光聚合起始劑(C)、及被較波長380nm為短波長側之光激發而發出波長380nm~550nm之光之波長轉換劑(D)，其中：熱塑性樹脂(A)為如下之樹脂，其含有玻璃轉移溫度(Tg)未達0℃之單體a、玻璃轉移溫度(Tg)為0℃以上且未達80℃之單體b、玻璃轉移溫度(Tg)為80℃以上之單體c以a：b：c=10~40：90~35：0~25之莫耳比率進行共聚合而成且重量平均分子量為50000~400000之(甲基)丙烯酸酯共聚物或乙烯系共聚物，且波長390nm下之黏著片材之吸光度X與黏著片材之厚度Y滿足下述關係式(1)，式(1)...0.5≦X/Y≦12。A transparent adhesive sheet characterized by comprising an adhesive composition, said adhesive composition containing a thermoplastic resin (A), a cross-linking agent (B), and photopolymerized by photoreaction with light having a wavelength of at least 380 nm to 430 nm An initiator (C) and a wavelength conversion agent (D) which is excited by light having a shorter wavelength side than 380 nm and emits light having a wavelength of 380 nm to 550 nm. Among them, the thermoplastic resin (A) is the following resin, which contains glass transition Monomer a with a temperature (Tg) of less than 0 ° C, monomer b with a glass transition temperature (Tg) of 0 ° C or more and less than 80 ° C, and monomer c with a glass transition temperature (Tg) of more than 80 ° C. b: (meth) acrylic acid ester copolymer or ethylene-based copolymer having a molar ratio of 10 to 40: 90 to 35: 0 to 25 and copolymerized with a weight average molecular weight of 50,000 to 400,000, and a wavelength of 390 nm The absorbance X of the lower adhesive sheet and the thickness Y of the adhesive sheet satisfy the following relational expression (1), where the expression (1) ... 0.5 ≦ X / Y ≦ 12. 如請求項1之透明黏著片材，其中波長轉換劑(D)係相溶於熱塑性樹脂(A)之材料。The transparent adhesive sheet according to claim 1, wherein the wavelength conversion agent (D) is a material which is phase-soluble in the thermoplastic resin (A). 如請求項2之透明黏著片材，其中波長轉換劑(D)係相溶於熱塑性樹脂(A)之材料。The transparent adhesive sheet according to claim 2, wherein the wavelength conversion agent (D) is a material which is phase-soluble in the thermoplastic resin (A). 如請求項1之透明黏著片材，其中透明黏著片材具有於未交聯狀態下藉由加熱而軟化或流動之熱熔性，並且具有藉由光而進行交聯之光交聯性。For example, the transparent adhesive sheet of claim 1, wherein the transparent adhesive sheet has a hot-melt property that is softened or flows by heating in an uncrosslinked state, and has a light-crosslinking property that is crosslinked by light. 如請求項2之透明黏著片材，其中透明黏著片材具有於未交聯狀態下藉由加熱而軟化或流動之熱熔性，並且具有藉由光而進行交聯之光交聯性。For example, the transparent adhesive sheet of claim 2, wherein the transparent adhesive sheet has hot-meltability which is softened or flowed by heating in an uncrosslinked state, and has photocrosslinkability which is crosslinked by light. 如請求項1至6中任一項之透明黏著片材，其係於正背面一側或兩側具備剝離膜之黏著片材，且至少正背面一側之上述剝離膜係較波長380nm為短波長側之光之光線透過率為40%以下之膜。For example, the transparent adhesive sheet according to any one of claims 1 to 6, which is an adhesive sheet with a release film on one or both sides of the front and back sides, and the release film on at least the front and back sides is shorter than a wavelength of 380 nm Film with a light transmittance of 40% or less on the wavelength side.
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Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7197255B2 (en) * 2016-02-29 2022-12-27 三菱ケミカル株式会社 Transparent double-sided adhesive sheet and adhesive sheet laminate
JP6389198B2 (en) * 2016-02-22 2018-09-12 リンテック株式会社 Adhesive sheet, display body, and production method thereof
CN110023357A (en) * 2016-12-02 2019-07-16 三菱化学株式会社 Photocurable composition, bonding sheet, bonding laminate, solidfied material, image display device constitute and use laminated body and image display device
JP7013822B2 (en) * 2016-12-02 2022-02-01 三菱ケミカル株式会社 Adhesive resin composition and adhesive sheet
US10283476B2 (en) 2017-03-15 2019-05-07 Immunolight, Llc. Adhesive bonding composition and electronic components prepared from the same
JP6866881B2 (en) * 2017-08-08 2021-04-28 三菱ケミカル株式会社 Method for manufacturing photo-curable adhesive sheet laminate, photo-curable adhesive sheet laminate, and method for manufacturing image display panel laminate
KR102566973B1 (en) * 2017-08-08 2023-08-14 미쯔비시 케미컬 주식회사 Photocurable pressure-sensitive adhesive sheet, photocurable pressure-sensitive adhesive sheet laminate, production method for photocurable pressure-sensitive adhesive sheet laminate, and production method for image display panel laminate
JP6866880B2 (en) * 2017-08-08 2021-04-28 三菱ケミカル株式会社 Photo-curable adhesive sheet
JP6360605B1 (en) * 2017-08-30 2018-07-18 リンテック株式会社 Manufacturing method of display body
KR102335316B1 (en) * 2017-12-27 2021-12-06 주식회사 엘지화학 Adhesive composition and protection film using the same
KR102024079B1 (en) * 2018-01-03 2019-09-24 주식회사 테이팩스 An optical adhesive agent curable by ultraviolet, and laminates comprising the same
JP6438165B1 (en) * 2018-06-22 2018-12-12 リンテック株式会社 Adhesive sheet and display
WO2020137111A1 (en) * 2018-12-25 2020-07-02 株式会社スリーボンド Curable resin composition, fuel cell, and sealing method
TW202128785A (en) * 2019-07-31 2021-08-01 日商積水保力馬科技股份有限公司 Photocurable resin composition
WO2022034885A1 (en) * 2020-08-11 2022-02-17 王子ホールディングス株式会社 Adhesive sheet, adhesive sheet with release sheet, multilayer body, and method for producing multilayer body
JP2022032291A (en) * 2020-08-11 2022-02-25 王子ホールディングス株式会社 Adhesive sheet, adhesive sheet with release sheet, multilayer body, and method for producing multilayer body
JP7385796B1 (en) * 2023-01-19 2023-11-24 東洋インキＳｃホールディングス株式会社 Adhesive composition for decorative sheet, decorative sheet, decorative structure and manufacturing method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201418404A (en) * 2012-10-15 2014-05-16 Hitachi Chemical Co Ltd Adhesive sheet for image display device, method for manufacturing image display device, and image display device

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101157723B1 (en) * 2007-05-28 2012-06-20 디아이씨 가부시끼가이샤 Removable adhesive sheet
TWI485214B (en) 2008-09-05 2015-05-21 Kyoritsu Chemical Co Ltd And a photohardenable resin composition for bonding an optical functional material
JP5716881B2 (en) 2008-10-04 2015-05-13 スリーボンドファインケミカル株式会社 Photocurable adhesive composition
JP5397944B2 (en) 2009-11-11 2014-01-22 日東電工株式会社 Phosphor-containing composite sheet
JP2011151094A (en) * 2010-01-20 2011-08-04 Toyo Ink Sc Holdings Co Ltd Solar cell module
EP2615600B1 (en) 2010-09-06 2018-03-14 Mitsubishi Chemical Corporation Method for producing laminate for configuring image display device, and image display device using the laminate
KR101279980B1 (en) 2010-12-29 2013-07-05 제일모직주식회사 Anisotropic conductive film composition and the anisotropic conductive film thereof
WO2013105162A1 (en) 2012-01-13 2013-07-18 日本化薬株式会社 Optical member, and ultraviolet-curable adhesive used in production of same
CN104114359B (en) 2012-01-13 2018-01-09 日本化药株式会社 Optical component and the ultraviolet curing adhesive for manufacturing the optical component
JP2015511256A (en) * 2012-02-01 2015-04-16 日東電工株式会社 Pressure-sensitive adhesive wavelength conversion tape to improve sunlight collection efficiency
JP5948075B2 (en) 2012-02-15 2016-07-06 株式会社寺岡製作所 Adhesive sheet and method for producing the same, adhesive sheet, photocurable adhesive composition, and optical member
JP2013184997A (en) 2012-03-06 2013-09-19 Hitachi Chemical Co Ltd Liquid photocurable resin composition, image display device using the same, and method of manufacturing the same
JP5901741B2 (en) * 2012-03-21 2016-04-13 日本化薬株式会社 Optical member and ultraviolet curable adhesive used in the production thereof
KR20130119165A (en) * 2012-04-23 2013-10-31 주식회사 이그잭스 Functional adhesive containing silica
CN104487534B (en) * 2012-07-11 2016-11-09 大自达电线股份有限公司 Hardening conductive adhesive composition, electromagnetic shielding film, conductive adhesive film, adhesive method and circuit base plate

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201418404A (en) * 2012-10-15 2014-05-16 Hitachi Chemical Co Ltd Adhesive sheet for image display device, method for manufacturing image display device, and image display device

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